Golf ball with soft feel

ABSTRACT

A golf ball comprising:
         (a) a core;   (b) an inner mantle layer;   (c) an intermediate mantle layer;   (d) an outer mantle layer; and   (e) at least one cover layer;   wherein the core has a PGA compression of less than 70, and the core/inner mantle layer/intermediate mantle layer combined construct has a PGA compression of at least 30.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/557,724, filed on Aug. 30, 2019, which is a continuation of U.S.application Ser. No. 15/809,826, which was filed Nov. 10, 2017, now U.S.Pat. No. 10,441,852, which is a continuation of U.S. application Ser.No. 15/221,245, which was filed Jul. 27, 2016, now abandoned, which is acontinuation of U.S. application Ser. No. 14/216,526, which was filedMar. 17, 2014, now U.S. Pat. No. 9,421,425, issued Aug. 23, 2016, whichis a continuation of U.S. application Ser. No. 13/619,721, filed Sep.14, 2012, now U.S. Pat. No. 8,715,113, issued May 6, 2014, which is acontinuation of U.S. application Ser. No. 12/343,090, filed Dec. 23,2008, now U.S. Pat. No. 8,357,060, issued Jan. 22, 2013, which claimsthe benefit of U.S. Provisional Application No. 61/009,427, filed Dec.28, 2007, all of which are incorporated herein by reference in theirentirety.

FIELD

This disclosure relates to golf balls.

BACKGROUND

“Multi-layer” golf balls generally include at least three “pieces”—acentral core and at least two layers surrounding the core. A multi-layerball can offer several advantages and disadvantages. However, thespecific advantages and disadvantages potentially provided by a specificcontemplated design are unpredictable due to the complex nature of thephysical interaction between the various materials used in the core andthe layers.

SUMMARY

Disclosed herein are various golf ball embodiments, and methods formaking the golf balls.

In one embodiment, the golf ball comprises:

-   -   (a) a core;    -   (b) an inner mantle layer;    -   (c) an intermediate mantle layer;    -   (d) an outer mantle layer; and    -   (e) at least one cover layer;    -   wherein the core has a PGA compression of less than 70, and the        core/inner mantle layer/intermediate mantle layer combined        construct has a PGA compression of at least 30.

In another embodiment, the golf ball comprises:

-   -   (a) a core material having a PGA compression of less than 70 and        a material flexural modulus of less than 20 kpsi;    -   (b) an inner mantle layer material;    -   (c) an intermediate mantle layer material;    -   (d) an outer mantle layer material; and    -   (e) at least one cover layer material;    -   wherein the material of each of (a), (b), (c) and (d) have a        material flexural modulus and the material flexural modulus of        each of (a), (b), (c) and (d) increases from the core material        to the outer mantle layer material such that each successive        layer between the core material and the outer mantle layer        material has a flexural modulus that is greater relative to the        immediately adjacent inner layer material.

According to a further embodiment, there is disclosed a five-piece golfball comprising:

-   -   (a) a core material having a flexural modulus of less than 15        kpsi;    -   (b) an inner mantle layer material adjacent to the core        material, wherein the inner mantle layer material has a flexural        modulus of 2-35 kpsi;    -   (c) an intermediate mantle layer material adjacent to the inner        mantle layer material, wherein the intermediate mantle layer        material has a flexural modulus of 10-50 kpsi;    -   (d) an outer mantle layer material adjacent to the intermediate        mantle layer material, wherein the outer mantle layer material        has a flexural modulus of 30-110 kpsi; and    -   (e) an outer cover layer material.

Another embodiment is a golf ball comprising:

-   -   (a) a core having a PGA compression of less than 40;    -   (b) an inner mantle layer;    -   (c) an intermediate mantle layer;    -   (d) an outer mantle layer; and    -   (e) an outer cover layer;    -   wherein the golf ball has sufficient impact durability and a        golf ball frequency of <4000 Hz.

The foregoing will become more apparent from the following detaileddescription, which proceeds with reference to the accompanying figures.

BRIEF DESCRIPTION OF THE DRAWINGS

Referring to the drawing in FIG. 1 there is illustrated a golf ball 1,which comprises a solid center or core 2, formed as a solid body and inthe shape of the sphere, an inner mantle layer 3, disposed on thespherical core, an intermediate mantle layer 4, disposed on the innermantle layer 3, an outer mantle layer 5 disposed on the intermediatemantle layer 4, and a cover layer 6 disposed on the outer mantle layer5. In other words, the intermediate mantle layer 4 is located betweenthe inner mantle layer 3 and the outer mantle layer 5.

DETAILED DESCRIPTION

For ease of understanding, the following terms used herein are describedbelow in more detail:

The term “core” refers to the elastic center of a golf ball, which mayhave a unitary construction. Alternatively the core itself may have alayered construction having a spherical “center” and additional “corelayers,” which such layers usually being made of the same material asthe core center.

The term “cover layer” or “cover” refers to any layer or layers of thegolf ball adjacent to, and preferably surrounding (partially surroundingor entirely surrounding), the outermost mantle layer. The term “outercover layer” refers to the outermost cover layer of the golf ball; thisis the layer that is directly in contact with paint and/or ink on thesurface of the golf ball and on which the dimple pattern is placed. Theterm outer cover layer as used herein is used interchangeably with theterm “outer cover”. In some embodiments, the cover may include two ormore layers. In these embodiments, the term “inner cover layer” or“inner cover” refers to any cover layer positioned between the outermostmantle layer and the outer cover layer.

The term “mantle layer” or “mantle” refers to any layer(s) in a golfball disposed between the core and the cover layer(s). The mantle layermay be in the shape of a hollow, thin-skinned sphere that may or may notinclude inward or outward protrusions (e.g., the intermediate layer maybe of substantially the same thickness around its entire curvature). Amantle layer may partially or entirely surround the core. In the case ofa ball with two or more mantle layers, the term “inner mantle” or “innermantle layer” refers to the mantle layer of the ball that is disposednearest to the core. Again, in the case of a ball with two or moremantle layers, the term “outer mantle” or “outer mantle layer” refers tothe mantle layer of the ball that is disposed nearest to the outer coverlayer.

The term “bimodal polymer” refers to a polymer comprising two mainfractions and more specifically to the form of the polymers molecularweight distribution curve, i.e., the appearance of the graph of thepolymer weight fraction as function of its molecular weight. When themolecular weight distribution curves from these fractions aresuperimposed into the molecular weight distribution curve for the totalresulting polymer product, that curve will show two maxima or at leastbe distinctly broadened in comparison with the curves for the individualfractions. Such a polymer product is called bimodal. It is to be notedhere that also the chemical compositions of the two fractions may bedifferent.

Similarly the term “unimodal polymer” refers to a polymer comprising onemain fraction and more specifically to the form of the polymer'smolecular weight distribution curve, i.e., the molecular weightdistribution curve for the total polymer product shows only a singlemaximum.

A “high acid ionomer” generally refers to an ionomer resin or polymerthat includes more than about 16 wt. %, more particularly more thanabout 19 wt. %, of unsaturated mono- or dicarboxylic acids units basedon the weight of resin or polymer.

The term “hydrocarbyl” includes any aliphatic, cycloaliphatic, aromatic,aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphaticsubstituted aromatic, or cycloaliphatic substituted aromatic groups. Thealiphatic or cycloaliphatic groups are preferably saturated. Likewise,the term “hydrocarbyloxy” means a hydrocarbyl group having an oxygenlinkage between it and the carbon atom to which it is attached.

The term “(meth)acrylic acid copolymers” refers to copolymers ofmethacrylic acid and/or acrylic acid.

The term “(meth)acrylate” refers to an ester of methacrylic acid and/oracrylic acid.

The term “partially neutralized” refers to an ionomer with a degree ofneutralization of less than 100 percent.

“Prepolymer” refers to any material that can be further processed toform a final polymer material of a manufactured golf ball, such as, byway of example and not limitation, a polymerized or partiallypolymerized material that can undergo additional processing, such ascrosslinking.

The term “polyurea” as used herein refers to materials prepared byreaction of a diisocyanate with a polyamine

The term “polyurethane” as used herein refers to materials prepared byreaction of a diisocyanate with a polyol.

A “specialty propylene elastomer” includes a thermoplasticpropylene-ethylene copolymer composed of a majority amount of propyleneand a minority amount of ethylene. These copolymers have at leastpartial crystallinity due to adjacent isotactic propylene units.Although not bound by any theory, it is believed that the crystallinesegments are physical crosslinking sites at room temperature, and athigh temperature (i.e., about the melting point), the physicalcrosslinking is removed and the copolymer is easy to process. Accordingto one embodiment, a specialty propylene elastomer includes at leastabout 50 mole % propylene co-monomer. Specialty propylene elastomers canalso include functional groups such as maleic anhydride, glycidyl,hydroxyl, and/or carboxylic acid. Suitable specialty propyleneelastomers include propylene-ethylene copolymers produced in thepresence of a metallocene catalyst. More specific examples of specialtypropylene elastomers are illustrated below.

A “terpolymeric ionomer” generally refers to ionomers of polymers ofgeneral formula, E/X/Y polymer, wherein E is ethylene, X is a C₃ to C₈α,β ethylenically unsaturated carboxylic acid, such as acrylic ormethacrylic acid, and Y is a softening comonomer.

A “thermoplastic” is generally defined as a material that is capable ofsoftening or melting when heated and of hardening again when cooled.Thermoplastic polymer chains often are not cross-linked or are lightlycrosslinked using a chain extender, but the term “thermoplastic” as usedherein may refer to materials that initially act as thermoplastics, suchas during an initial extrusion process or injection molding process, butwhich also may be crosslinked, such as during a compression molding stepto form a final structure.

A “thermoset” is generally defined as a material that crosslinks orcures via interaction with as crosslinking or curing agent. Crosslinkingmay be induced by energy, such as heat (generally above 200° C.),through a chemical reaction (by reaction with a curing agent), or byirradiation. The resulting composition remains rigid when set, and doesnot soften with heating. Thermosets have this property because thelong-chain polymer molecules cross-link with each other to give a rigidstructure. A thermoset material cannot be melted and re-molded after itis cured. Thus thermosets do not lend themselves to recycling unlikethermoplastics, which can be melted and re-molded.

The term “thermoplastic polyurethane” refers to a material prepared byreaction of a prepared by reaction of a diisocyanate with a polyol, andoptionally addition of a chain extender.

The term “thermoplastic polyurea” refers to a material prepared byreaction of a prepared by reaction of a diisocyanate with a polyamine,with optionally addition of a chain extender.

The term “thermoset polyurethane” refers to a material prepared byreaction of a diisocyanate with a polyol, and a curing agent.

The term “thermoset polyurea” refers to a material prepared by reactionof a diisocyanate with a polyamine, and a curing agent.

A “urethane prepolymer” is the reaction product of diisocyanate and apolyol.

A “urea prepolymer” is the reaction product of a diisocyanate and apolyamine

The term “unimodal polymer” refers to a polymer comprising one mainfraction and more specifically to the form of the polymer's molecularweight distribution curve, i.e., the molecular weight distribution curvefor the total polymer product shows only a single maximum.

The above term descriptions are provided solely to aid the reader, andshould not be construed to have a scope less than that understood by aperson of ordinary skill in the art or as limiting the scope of theappended claims.

The singular terms “a,” “an,” and “the” include plural referents unlesscontext clearly indicates otherwise. The word “comprises” indicates“includes.” It is further to be understood that all molecular weight ormolecular mass values given for compounds are approximate, and areprovided for description. The materials, methods, and examples areillustrative only and not intended to be limiting. Unless otherwiseindicated, description of components in chemical nomenclature refers tothe components at the time of addition to any combination specified inthe description, but does not necessarily preclude chemical interactionsamong the components of a mixture once mixed.

Any numerical values recited herein include all values from the lowervalue to the upper value in increments of one unit provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent or a value of a process variable is from 1 to 90, preferablyfrom 20 to 80, more preferably from 30 to 70, it is intended that valuessuch as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc., are expresslyenumerated in this specification. For values, which have less than oneunit difference, one unit is considered to be 0.1, 0.01, 0.001, or0.0001 as appropriate. Thus all possible combinations of numericalvalues between the lowest value and the highest value enumerated hereinare said to be expressly stated in this application.

It is desirable to have a relatively hard outer mantle layer (e.g., anouter mantle layer having a material Shore D hardness of at least 65,and a flexural modulus of at least 65 kpsi) to provide increaseddurability to a golf ball. However, it has now been discovered that suchan outer mantle layer tends to suffer durability failures if the golfball also has a relatively low core PGA compression. For example,durability failures occur in three-piece golf balls (core, outer mantle,outer cover) that have a core PGA compression of less than 60 and anouter mantle material Shore D hardness of 65 and a flexural modulus of65 kpsi. Durability failures occur in four-piece golf balls (core, innermantle, outer mantle, outer cover) that have core PGA compression ofless than 45 and an outer mantle material Shore D hardness of 65 and aflexural modulus of 65 kpsi.

In one embodiment, disclosed herein are golf balls that include a mantleconstruction that can maintain the durability of the golf ball whileretaining the soft feel of a low core PGA compression. For example, thecore/inner mantle layer/intermediate mantle layer combined construct mayhave a PGA compression of at least 30, more particularly of at least 40.The phrase “core/inner mantle layer/intermediate mantle layer combinedconstruct” refers to a construct formed from the core, the inner mantlelayer and the intermediate mantle layer (i.e., an inner constructlocated within the outer mantle layer). The PGA compression of thisinner combined construct is measured. In certain examples, the PGAcompression may be at least 50, more particularly at least 60. In otherexamples, the PGA compression of the inner combined construct is 30 to70. The inner combined construct provides extra support for the outermantle layer to minimize cracking or other damage of the cover layerand/or outer mantle layer. The ball can include more than one innermantle layer and/or more than one intermediate mantle layer.

The golf balls disclosed herein are at least five-piece golf balls. Inother words, the golf balls include at least five separate layers(including the core). The golf ball may include multiple mantle layersand/or multiple cover layers.

In certain embodiments, the flexural modulus of each of the core and themantle layer materials increases from the core to the outermost mantlelayer. In other words, an illustrative golf ball satisfies an increasingflexural modulus gradient relationship of: FM(core)<FM(innerM)<FM(intermediate M)<FM(outer M). The flexural modulus of eachsuccessive layer may exceed, for example, the immediate inner layer byat least 2 kpsi, more particularly at least 3 kpsi, and mostparticularly, 5 kpsi.

In certain embodiments, the material Shore D hardness of each of thecore and the layer materials increases from the core to the outermostmantle layer. In other words, an illustrative golf ball satisfies anincreasing material Shore D hardness gradient relationship of:

H(CR)<H(inner M)<H(R)<H(outer M).

In certain embodiments, the “soft feel” of the golf ball may be measuredby having a specific sound frequency and loudness which imparts a softeroverall sound/feel to the golf ball. For example, the golf ball may havea golf ball frequency of less than 4000 Hz, more particularly less than3600 Hz, and most particularly less than 3400 Hz. The golf ball may havea sound pressure level, S, of less than 81.5 dB, more particularly lessthan 81 dB, and most particularly less than 80.5 dB. Frequency is ameasure of the “pitch” of the sound, and true loudness is measured indecibel (db) levels. Balls can be hit or tested at 30 yard shots forsound and pitch and subsequently this translates into ball feel that thegolfer experiences. By plotting db levels v. frequency, you obtain aratio of “feel”.

A. Polymer Components

The core, mantle layer(s) and cover layer(s) may each include one ormore of the following polymers.

Such polymers include synthetic and natural rubbers, thermoset polymerssuch as thermoset polyurethanes and thermoset polyureas, as well asthermoplastic polymers including thermoplastic elastomers such asunimodal ethylene/carboxylic acid copolymers, unimodalethylene/carboxylic acid/carboxylate terpolymers, bimodalethylene/carboxylic acid copolymers, bimodal ethylene/carboxylicacid/carboxylate terpolymers, unimodal ionomers, bimodal ionomers,modified unimodal ionomers, modified bimodal ionomers, thermoplasticpolyurethanes, thermoplastic polyureas, polyesters, copolyesters,polyamides, copolyamides, polycarbonates, polyolefins, polyphenyleneoxide, polyphenylene sulfide, diallyl phthalate polymer, polyimides,polyvinyl chloride, polyamide-ionomer, polyurethane-ionomer, polyvinylalcohol, polyarylate, polyacrylate, polyphenylene ether, impact-modifiedpolyphenylene ether, polystyrene, high impact polystyrene,acrylonitrile-butadiene-styrene copolymer styrene-acrylonitrile (SAN),acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S/MA)polymer, styrenic copolymer, functionalized styrenic copolymer,functionalized styrenic terpolymer, styrenic terpolymer, cellulosepolymer, liquid crystal polymer (LCP), ethylene-propylene-dieneterpolymer (EPDM), ethylene-vinyl acetate copolymers (EVA),ethylene-propylene copolymer, ethylene vinyl acetate, polyurea, andpolysiloxane and any and all combinations thereof. One example isParaloid EXL 2691A which is a methacrylate-butadiene-styrene (MBS)impact modifier available from Rohm & Haas Co.

More particularly, the synthetic and natural rubber polymers may includethe traditional rubber components used in golf ball applicationsincluding, both natural and synthetic rubbers, such ascis-1,4-polybutadiene, trans-1,4-polybutadiene, 1,2-polybutadiene,cis-polyisoprene, trans-polyisoprene, polychloroprene, polybutylene,styrene-butadiene rubber, styrene-butadiene-styrene block copolymer andpartially and fully hydrogenated equivalents, styrene-isoprene-styreneblock copolymer and partially and fully hydrogenated equivalents,nitrile rubber, silicone rubber, and polyurethane, as well as mixturesof these. Polybutadiene rubbers, especially 1,4-polybutadiene rubberscontaining at least 40 mol %, and more preferably 80 to 100 mol % ofcis-1,4 bonds, are preferred because of their high rebound resilience,moldability, and high strength after vulcanization. The polybutadienecomponent may be synthesized by using rare earth-based catalysts,nickel-based catalysts, or cobalt-based catalysts, conventionally usedin this field. Polybutadiene obtained by using lanthanum rareearth-based catalysts usually employ a combination of a lanthanum rareearth (atomic number of 57 to 71)-compound, but particularly preferredis a neodymium compound.

The 1,4-polybutadiene rubbers have a molecular weight distribution(Mw/Mn) of from about 1.2 to about 4.0, preferably from about 1.7 toabout 3.7, even more preferably from about 2.0 to about 3.5, mostpreferably from about 2.2 to about 3.2. The polybutadiene rubbers have aMooney viscosity (ML₁₊₄ (100° C.)) of from about 20 to about 80,preferably from about 30 to about 70, even more preferably from about 30to about 60, most preferably from about 35 to about 50. The term “Mooneyviscosity” used herein refers in each case to an industrial index ofviscosity as measured with a Mooney viscometer, which is a type ofrotary plastometer (see JIS K6300). This value is represented by thesymbol ML₁₊₄ (100° C.), wherein “M” stands for Mooney viscosity, “L”stands for large rotor (L-type), “1+4” stands for a pre-heating time of1 minute and a rotor rotation time of 4 minutes, and “100° C.” indicatesthat measurement was carried out at a temperature of 100° C.

Examples of 1,2-polybutadienes having differing tacticity, all of whichare suitable as unsaturated polymers for use in the presently disclosedcompositions, are atactic 1,2-polybutadiene, isotactic1,2-polybutadiene, and syndiotactic 1,2-polybutadiene. Syndiotactic1,2-polybutadiene having crystallinity suitable for use as anunsaturated polymer in the presently disclosed compositions arepolymerized from a 1,2-addition of butadiene. The presently disclosedgolf balls may include syndiotactic 1,2-polybutadiene havingcrystallinity and greater than about 70% of 1,2-bonds, more preferablygreater than about 80% of 1,2-bonds, and most preferably greater thanabout 90% of 1,2-bonds. Also, the 1,2-polybutadiene may have a meanmolecular weight between about 10,000 and about 350,000, more preferablybetween about 50,000 and about 300,000, more preferably between about80,000 and about 200,000, and most preferably between about 10,000 andabout 150,000. Examples of suitable syndiotactic 1,2-polybutadieneshaving crystallinity suitable for use in golf balls are sold under thetrade names RB810, RB820, and RB830 by JSR Corporation of Tokyo, Japan.These have more than 90% of 1,2 bonds, a mean molecular weight ofapproximately 120,000, and crystallinity between about 15% and about30%.

Examples of olefinic thermoplastic elastomers includemetallocene-catalyzed polyolefins, ethylene-octene copolymer,ethylene-butene copolymer, and ethylene-propylene copolymers all with orwithout controlled tacticity as well as blends of polyolefins havingethyl-propylene-non-conjugated diene terpolymer, rubber-based copolymer,and dynamically vulcanized rubber-based copolymer. Examples of theseinclude products sold under the trade names SANTOPRENE, DYTRON,VISAFLEX, and VYRAM by Advanced Elastomeric Systems of Houston, Tex.,and SARLINK by DSM of Haarlen, the Netherlands.

Examples of rubber-based thermoplastic elastomers include multiblockrubber-based copolymers, particularly those in which the rubber blockcomponent is based on butadiene, isoprene, or ethylene/butylene. Thenon-rubber repeating units of the copolymer may be derived from anysuitable monomers, including meth(acrylate) esters, such as methylmethacrylate and cyclohexylmethacrylate, and vinyl arylenes, such asstyrene. Examples of styrenic copolymers are resins manufactured byKraton Polymers (formerly of Shell Chemicals) under the trade namesKRATON D (for styrene-butadiene-styrene and styrene-isoprene-styrenetypes) and KRATON G (for styrene-ethylene-butylene-styrene andstyrene-ethylene-propylene-styrene types) and Kuraray under the tradename SEPTON. Examples of randomly distributed styrenic polymers includeparamethylstyrene-isobutylene (isobutene) copolymers developed byExxonMobil Chemical Corporation and styrene-butadiene random copolymersdeveloped by Chevron Phillips Chemical Corp.

Examples of copolyester thermoplastic elastomers include polyether esterblock copolymers, polylactone ester block copolymers, and aliphatic andaromatic dicarboxylic acid copolymerized polyesters. Polyether esterblock copolymers are copolymers comprising polyester hard segmentspolymerized from a dicarboxylic acid and a low molecular weight diol,and polyether soft segments polymerized from an alkylene glycol having 2to 10 atoms. Polylactone ester block copolymers are copolymers havingpolylactone chains instead of polyether as the soft segments discussedabove for polyether ester block copolymers. Aliphatic and aromaticdicarboxylic copolymerized polyesters are copolymers of an acidcomponent selected from aromatic dicarboxylic acids, such asterephthalic acid and isophthalic acid, and aliphatic acids having 2 to10 carbon atoms with at least one diol component, selected fromaliphatic and alicyclic diols having 2 to 10 carbon atoms. Blends ofaromatic polyester and aliphatic polyester also may be used for these.Examples of these include products marketed under the trade names HYTRELby E.I. DuPont de Nemours & Company, and SKYPEL by S.K. Chemicals ofSeoul, South Korea.

Examples of other thermoplastic elastomers suitable as additionalpolymer components include those having functional groups, such ascarboxylic acid, maleic anhydride, glycidyl, norbonene, and hydroxylfunctionalities. An example of these includes a block polymer having atleast one polymer block A comprising an aromatic vinyl compound and atleast one polymer block B comprising a conjugated diene compound, andhaving a hydroxyl group at the terminal block copolymer, or itshydrogenated product. An example of this polymer is sold under the tradename SEPTON HG-252 by Kuraray Company of Kurashiki, Japan. Otherexamples of these include: maleic anhydride functionalized triblockcopolymer consisting of polystyrene end blocks andpoly(ethylene/butylene), sold under the trade name KRATON FG 1901X byShell Chemical Company; maleic anhydride modified ethylene-vinyl acetatecopolymer, sold under the trade name FUSABOND by E.I. DuPont de Nemours& Company; ethylene-isobutyl acrylate-methacrylic acid terpolymer, soldunder the trade name NUCREL by E.I. DuPont de Nemours & Company;ethylene-ethyl acrylate-methacrylic anhydride terpolymer, sold under thetrade name BONDINE AX 8390 and 8060 by Sumitomo Chemical Industries;brominated styrene-isobutylene copolymers sold under the trade nameBROMO XP-50 by Exxon Mobil Corporation; and resins having glycidyl ormaleic anhydride functional groups sold under the trade name LOTADER byElf Atochem of Puteaux, France.

Another example of a polymer for making any of the mantle layers orcover layer is blend of a polyamide (which may be a polyamide asdescribed above) with a functional polymer modifier of the polyamide.The functional polymer modifier of the polyamide can include copolymersor terpolymers having a glycidyl group, hydroxyl group, maleic anhydridegroup or carboxylic group, collectively referred to as functionalizedpolymers. These copolymers and terpolymers may comprise an α-olefin.Examples of suitable α-olefins include ethylene, propylene, 1-butene,1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-l-petene,3-methyl-l-pentene, 1-octene, 1-decene-, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene,1-hexacocene, 1-octacocene, and 1-triacontene. One or more of theseα-olefins may be used.

Examples of suitable glycidyl groups in copolymers or terpolymers in thepolymeric modifier include esters and ethers of aliphatic glycidyl, suchas allylglycidylether, vinylglycidylether, glycidyl maleate anditaconatem glycidyl acrylate and methacrylate, and also alicyclicglycidyl esters and ethers, such as 2-cyclohexene-l-glycidylether,cyclohexene-4,5 diglyxidylcarboxylate, cyclohexene-4-glycidylcarobxylate, 5-norboenene-2-methyl-2-glycidyl carboxylate, andendocis-bicyclo(2,2,1)-5-heptene-2,3-diglycidyl dicarboxylate. Thesepolymers having a glycidyl group may comprise other monomers, such asesters of unsaturated carboxylic acid, for example, alkyl(meth)acrylatesor vinyl esters of unsaturated carboxylic acids. Polymers having aglycidyl group can be obtained by copolymerization or graftpolymerization with homopolymers or copolymers.

Examples of suitable terpolymers having a glycidyl group include LOTADERAX8900 and AX8920, marketed by Atofina Chemicals, ELVALOY marketed byE.I. Du Pont de Nemours & Co., and REXPEARL marketed by NipponPetrochemicals Co., Ltd. Additional examples of copolymers comprisingepoxy monomers and which are suitable for use within the scope of thepresent invention include styrene-butadiene-styrene block copolymers inwhich the polybutadiene block contains epoxy group, andstyrene-isoprene-styrene block copolymers in which the polyisopreneblock contains epoxy. Commercially available examples of these epoxyfunctional copolymers include ESBS A1005, ESBS A1010, ESBS A1020, ESBSAT018, and ESBS AT019, marketed by Daicel Chemical Industries, Ltd.

Examples of polymers or terpolymers incorporating a maleic anhydridegroup suitable for use within the scope of the present invention includemaleic anhydride-modified ethylene-propylene copolymers, maleicanhydride-modified ethylene-propylene-diene terpolymers, maleicanhydride-modified polyethylenes, maleic anhydride-modifiedpolypropylenes, ethylene-ethylacrylate-maleic anhydride terpolymers, andmaleic anhydride-indene-styrene-cumarone polymers. Examples ofcommercially available copolymers incorporating maleic anhydrideinclude: BONDINE, marketed by Sumitomo Chemical Co., such as BONDINEAX8390, an ethylene-ethyl acrylate-maleic anhydride terpolymer having acombined ethylene acrylate and maleic anhydride content of 32% byweight, and BONDINE TX TX8030, an ethylene-ethyl acrylate-maleicanhydride terpolymer having a combined ethylene acrylate and maleicanhydride content of 15% by weight and a maleic anhydride content of 1%to 4% by weight; maleic anhydride-containing LOTADER 3200, 3210, 6200,8200, 3300, 3400, 3410, 7500, 5500, 4720, and 4700, marketed by AtofinaChemicals; EXXELOR VA1803, a maleic anyhydride-modifiedethylene-propylene copolymer having a maleic anyhydride content of 0.7%by weight, marketed by Exxon Chemical Co.; and KRATON FG 1901X, a maleicanhydride functionalized triblock copolymer having polystyrene endblocksand poly(ethylene/butylene) midblocks, marketed by Shell Chemical.

Preferably the functional polymer component for blending with apolyamide is a maleic anhydride grafted polymers preferably maleicanhydride grafted polyolefins (for example, Exxellor VA1803).

Styrenic block copolymers are copolymers of styrene with butadiene,isoprene, or a mixture of the two. Additional unsaturated monomers maybe added to the structure of the styrenic block copolymer as needed forproperty modification of the resulting SBC/urethane copolymer. Thestyrenic block copolymer can be a diblock or a triblock styrenicpolymer. Examples of such styrenic block copolymers are described in,for example, U.S. Pat. No. 5,436,295 to Nishikawa et al. The styrenicblock copolymer can have any known molecular weight for such polymers,and it can possess a linear, branched, star, dendrimeric or combinationmolecular structure. The styrenic block copolymer can be unmodified byfunctional groups, or it can be modified by hydroxyl group, carboxylgroup, or other functional groups, either in its chain structure or atone or more terminus. The styrenic block copolymer can be obtained usingany common process for manufacture of such polymers. The styrenic blockcopolymers also may be hydrogenated using well-known methods to obtain apartially or fully saturated diene monomer block.

Other preferred materials suitable for use as additional polymers in thepresently disclosed compositions include polyester thermoplasticelastomers marketed under the tradename SKYPEL™ by SK Chemicals of SouthKorea, or diblock or triblock copolymers marketed under the tradenameSEPTON™ by Kuraray Corporation of Kurashiki, Japan, and KRATON™ byKraton Polymers Group of Companies of Chester, United Kingdom. Forexample, SEPTON HG 252 is a triblock copolymer, which has polystyreneend blocks and a hydrogenated polyisoprene midblock and has hydroxylgroups at the end of the polystyrene blocks. HG-252 is commerciallyavailable from Kuraray America Inc. (Houston, Tex.).

Additional other polymer components include polyalkenamers as described,for example, in US-2006-0166762-A1, which is incorporated herein byreference in its entirety. Examples of suitable polyalkenamer rubbersare polypentenamer rubber, polyheptenamer rubber, polyoctenamer rubber,polydecenamer rubber and polydodecenamer rubber. For further detailsconcerning polyalkenamer rubber, see Rubber Chem. & Tech., Vol. 47, page511-596, 1974, which is incorporated herein by reference. Polyoctenamerrubbers are commercially available from Huls A G of Marl, Germany, andthrough its distributor in the U.S., Creanova Inc. of Somerset, N.J.,and sold under the trademark VESTENAMER®. Two grades of the VESTENAMER®trans-polyoctenamer are commercially available: VESTENAMER 8012designates a material having a trans-content of approximately 80% (and acis-content of 20%) with a melting point of approximately 54° C.; andVESTENAMER 6213 designates a material having a trans-content ofapproximately 60% (cis-content of 40%) with a melting point ofapproximately 30° C. Both of these polymers have a double bond at everyeighth carbon atom in the ring.

If a polyalkenamer rubber is present, the polyalkenamer rubberpreferably contains from about 50 to about 99, preferably from about 60to about 99, more preferably from about 65 to about 99, even morepreferably from about 70 to about 90 percent of its double bonds in thetrans-configuration. The preferred form of the polyalkenamer has a transcontent of approximately 80%, however, compounds having other ratios ofthe cis- and trans-isomeric forms of the polyalkenamer can also beobtained by blending available products for use in making thecomposition.

The polyalkenamer rubber has a molecular weight (as measured by GPC)from about 10,000 to about 300,000, preferably from about 20,000 toabout 250,000, more preferably from about 30,000 to about 200,000, evenmore preferably from about 50,000 to about 150,000.

The polyalkenamer rubber has a degree of crystallization (as measured byDSC secondary fusion) from about 5 to about 70, preferably from about 6to about 50, more preferably from about from 6.5 to about 50%, even morepreferably from about from 7 to about 45%.

More preferably, the polyalkenamer rubber is a polymer prepared bypolymerization of cyclooctene to form a trans-polyoctenamer rubber as amixture of linear and cyclic macromolecules.

A further example of a polymer is a specialty propylene elastomer asdescribed, for example, in US 2007/0238552 A1, and incorporated hereinby reference in its entirety. A specialty propylene elastomer includes athermoplastic propylene-ethylene copolymer composed of a majority amountof propylene and a minority amount of ethylene. These copolymers have atleast partial crystallinity due to adjacent isotactic propylene units.Although not bound by any theory, it is believed that the crystallinesegments are physical crosslinking sites at room temperature, and athigh temperature (i.e., about the melting point), the physicalcrosslinking is removed and the copolymer is easy to process. Accordingto one embodiment, a specialty propylene elastomer includes at leastabout 50 mole % propylene co-monomer. Specialty propylene elastomers canalso include functional groups such as maleic anhydride, glycidyl,hydroxyl, and/or carboxylic acid. Suitable specialty propyleneelastomers include propylene-ethylene copolymers produced in thepresence of a metallocene catalyst. More specific examples of specialtypropylene elastomers are illustrated below. Specialty propyleneelastomers are commercially available under the tradename VISTAMAXX fromExxonMobil Chemical.

Another example of an additional polymer component includes thethermoplastic polyurethanes, which are the reaction product of a diol orpolyol and an isocyanate, with or without a chain extender. Isocyanatesused for making the urethanes encompass diisocyanates andpolyisocyanates. Examples of suitable isocyanates include the following:trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylenediisocyanate, hexamethylene diisocyanate, ethylene diisocyanate,diethylidene diisocyanate, propylene diisocyanate, butylenediisocyanate, bitolylene diisocyanate, tolidine isocyanate, isophoronediisocyanate, dimeryl diisocyanate, dodecane-1,12-diisocyanate,1,10-decamethylene diisocyanate, cyclohexylene-1,2-diisocyanate,1-chlorobenzene-2,4-diisocyanate, furfurylidene diisocyanate,2,4,4-trimethyl hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate,1,3cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate,1,3-cyclobutane diisocyanate, 1,4-cyclohexane diisocyanate,4,4′-methylenebis(cyclohexyl isocyanate), 4,4′-methylenebis(phenylisocyanate), 1-methyl-2,4-cyclohexane diisocyanate,1-methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanato-methyl)cyclohexane,1,6-diisocyanato-2,2,4,4-tetra-methylhexane,1,6-diisocyanato-2,4,4-tetra-trimethylhexane,trans-cyclohexane-1,4-diisocyanate,3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexylisocyanate, dicyclohexylmethane 4,4′-diisocyanate,1,4-bis(isocyanatomethyl) cyclohexane, m-phenylene diisocyanate,m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-phenylenediisocyanate, p,p′-biphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenylenediisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate,3,3′-diphenyl-4,4′-biphenylene diisocyanate, 4,4′-biphenylenediisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate,1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate,1,5-tetrahydronaphthalene diisocyanate, meta-xylene diisocyanate,2,4-toluene diisocyanate, 2,4′-diphenylmethane diisocyanate,2,4-chlorophenylene diisocyanate, 4,4′-diphenylmethane diisocyanate,p,p′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, 2,2-diphenylpropane-4,4′-diisocyanate,4,4′-toluidine diisocyanate, dianisidine diisocyanate, 4,4′-diphenylether diisocyanate, 1,3-xylylene diisocyanate, 1,4-naphthylenediisocyanate, azobenzene-4,4′-diisocyanate, diphenylsulfone-4,4′-diisocyanate, triphenylmethane 4,4′,4″-triisocyanate,isocyanatoethyl methacrylate,3-isopropenyl-α,α-dimethylbenzyl-isocyanate, dichlorohexamethylenediisocyanate, ω, ω′-diisocyanato-1,4-diethylbenzene, polymethylenepolyphenylene polyisocyanate, polybutylene diisocyanate, isocyanuratemodified compounds, and carbodiimide modified compounds, as well asbiuret modified compounds of the above polyisocyanates. Each isocyanatemay be used either alone or in combination with one or more otherisocyanates. These isocyanate mixtures can include triisocyanates, suchas biuret of hexamethylene diisocyanate and triphenylmethanetriisocyanate, and polyisocyanates, such as polymeric diphenylmethanediisocyanate.

Polyols used for making the polyurethane in the copolymer includepolyester polyols, polyether polyols, polycarbonate polyols andpolybutadiene polyols. Polyester polyols are prepared by condensation orstep-growth polymerization utilizing diacids. Primary diacids forpolyester polyols are adipic acid and isomeric phthalic acids. Adipicacid is used for materials requiring added flexibility, whereas phthalicanhydride is used for those requiring rigidity. Some examples ofpolyester polyols include poly(ethylene adipate) (PEA), poly(diethyleneadipate) (PDA), poly(propylene adipate) (PPA), poly(tetramethyleneadipate) (PBA), poly(hexamethylene adipate) (PHA), poly(neopentyleneadipate) (PNA), polyols composed of 3-methyl-1,5-pentanediol and adipicacid, random copolymer of PEA and PDA, random copolymer of PEA and PPA,random copolymer of PEA and PBA, random copolymer of PHA and PNA,caprolactone polyol obtained by the ring-opening polymerization ofϵ-caprolactone, and polyol obtained by opening the ring ofβ-methyl-δ-valerolactone with ethylene glycol can be used either aloneor in a combination thereof. Additionally, polyester polyol may becomposed of a copolymer of at least one of the following acids and atleast one of the following glycols. The acids include terephthalic acid,isophthalic acid, phthalic anhydride, oxalic acid, malonic acid,succinic acid, pentanedioic acid, hexanedioic acid, octanedioic acid,nonanedioic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioicacid, dimer acid (a mixture), ρ-hydroxybenzoate, trimellitic anhydride,ϵ-caprolactone, and β-methyl-δ-valerolactone. The glycols includesethylene glycol, propylene glycol, butylene glycol, pentylene glycol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylene glycol,polyethylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, pentaerythritol, and 3-methyl-1,5-pentanediol.

Polyether polyols are prepared by the ring-opening additionpolymerization of an alkylene oxide (e.g. ethylene oxide and propyleneoxide) with an initiator of a polyhydric alcohol (e.g. diethyleneglycol), which is an active hydride. Specifically, polypropylene glycol(PPG), polyethylene glycol (PEG) or propylene oxide-ethylene oxidecopolymer can be obtained. Polytetramethylene ether glycol (PTMG) isprepared by the ring-opening polymerization of tetrahydrofuran, producedby dehydration of 1,4-butanediol or hydrogenation of furan.Tetrahydrofuran can form a copolymer with alkylene oxide. Specifically,tetrahydrofuran-propylene oxide copolymer or tetrahydrofuran-ethyleneoxide copolymer can be formed. A polyether polyol may be used eitheralone or in a mixture.

Polycarbonate polyol is obtained by the condensation of a known polyol(polyhydric alcohol) with phosgene, chloroformic acid ester, dialkylcarbonate or diallyl carbonate. A particularly preferred polycarbonatepolyol contains a polyol component using 1,6-hexanediol, 1,4-butanediol,1,3-butanediol, neopentylglycol or 1,5-pentanediol. A polycarbonatepolyol can be used either alone or in a mixture.

Polybutadiene polyol includes liquid diene polymer containing hydroxylgroups, and an average of at least 1.7 functional groups, and may becomposed of diene polymer or diene copolymer having 4 to 12 carbonatoms, or a copolymer of such diene with addition to polymerizableα-olefin monomer having 2 to 2.2 carbon atoms. Specific examples includebutadiene homopolymer, isoprene homopolymer, butadiene-styrenecopolymer, butadiene-isoprene copolymer, butadiene-acrylonitrilecopolymer, butadiene-2-ethyl hexyl acrylate copolymer, andbutadiene-n-octadecyl acrylate copolymer. These liquid diene polymerscan be obtained, for example, by heating a conjugated diene monomer inthe presence of hydrogen peroxide in a liquid reactant. A polybutadienepolyol can be used either alone or in a mixture.

As stated above, the urethane also may incorporate chain extenders.Non-limiting examples of these extenders include polyols, polyaminecompounds, and mixtures of these. Polyol extenders may be primary,secondary, or tertiary polyols. Specific examples of monomers of thesepolyols include: trimethylolpropane (TMP), ethylene glycol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol,2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2,5-hexanediol,2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, and2-ethyl-2-(hydroxymethyl)-1,3-propanediol.

Suitable polyamines that may be used as chain extenders include primary,secondary and tertiary amines; polyamines have two or more amines asfunctional groups. Examples of these include: aliphatic diamines, suchas tetramethylenediamine, pentamethylenediamine, hexamethylenediamine;alicyclic diamines, such as 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane; or aromatic diamines, such as 4,4′-methylenebis-2-chloroaniline, 2,2′,3,3′-tetrachloro-4,4′-diaminophenyl methane,p,p′-methylenedianiline, p-phenylenediamine or 4,4′-diaminodiphenyl; and2,4,6-tris(dimethylaminomethyl) phenol. Aromatic diamines have atendency to provide a stiffer product than aliphatic or cycloaliphaticdiamines A chain extender may be used either alone or in a mixture.

Polyurethanes or polyureas typically are prepared by reacting adiisocyanate with a polyol (in the case of polyurethanes) or with apolyamine (in the case of a polyurea). Thermoplastic polyurethanes orpolyureas may consist solely of this initial mixture or may be furthercombined with a chain extender to vary properties such as hardness ofthe thermoplastic. Thermoset polyurethanes or polyureas typically areformed by the reaction of a diisocyanate and a polyol or polyaminerespectively, and an additional crosslinking agent to crosslink or curethe material to result in a thermoset.

In what is known as a one-shot process, the three reactants,diisocyanate, polyol or polyamine, and optionally a chain extender or acuring agent, are combined in one step. Alternatively, a two-stepprocess may occur in which the first step involves reacting thediisocyanate and the polyol (in the case of polyurethane) or thepolyamine (in the case of a polyurea) to form a so-called prepolymer, towhich can then be added either the chain extender or the curing agent.This procedure is known as the prepolymer process.

In addition, although depicted as discrete component packages as above,it is also possible to control the degree of crosslinking, and hence thedegree of thermoplastic or thermoset properties in a final composition,by varying the stoichiometry not only of the diisocyanate-to-chainextender or curing agent ratio, but also the initialdiisocyanate-to-polyol or polyamine ratio. Of course in the prepolymerprocess, the initial diisocyanate-to-polyol or polyamine ratio is fixedon selection of the required prepolymer.

Finally, in addition to discrete thermoplastic or thermoset materials,it also is possible to modify a thermoplastic polyurethane or polyureacomposition by introducing materials in the composition that undergosubsequent curing after molding the thermoplastic to provide propertiessimilar to those of a thermoset. For example, Kim in U.S. Pat. No.6,924,337, the entire contents of which are hereby incorporated byreference, discloses a thermoplastic urethane or urea compositionoptionally comprising chain extenders and further comprising a peroxideor peroxide mixture, which can then undergo post curing to result in athermoset.

Also, Kim et al. in U.S. Pat. No. 6,939,924, the entire contents ofwhich are hereby incorporated by reference, discloses a thermoplasticurethane or urea composition, optionally also comprising chainextenders, that is prepared from a diisocyanate and a modified orblocked diisocyanate which unblocks and induces further cross linkingpost extrusion. The modified isocyanate preferably is selected from thegroup consisting of: isophorone diisocyanate (IPDI)-based uretdione-typecrosslinker; a combination of a uretdione adduct of IPDI and a partiallye-caprolactam-modified IPDI; a combination of isocyanate adductsmodified by e-caprolactam and a carboxylic acid functional group; acaprolactam-modified Desmodur diisocyanate; a Desmodur diisocyanatehaving a 3,5-dimethyl pyrazole modified isocyanate; or mixtures ofthese.

Finally, Kim et al. in U.S. Pat. No. 7,037,985 B2, the entire contentsof which are hereby incorporated by reference, discloses thermoplasticurethane or urea compositions further comprising a reaction product of anitroso compound and a diisocyanate or a polyisocyanate. The nitrosoreaction product has a characteristic temperature at which it decomposesto regenerate the nitroso compound and diisocyanate or polyisocyanate.Thus, by judicious choice of the post-processing temperature, furthercrosslinking can be induced in the originally thermoplastic compositionto provide thermoset-like properties.

Any isocyanate available to one of ordinary skill in the art is suitablefor use according to the invention. Isocyanates for use with the presentinvention include, but are not limited to, aliphatic, cycloaliphatic,aromatic aliphatic, aromatic, any derivatives thereof, and combinationsof these compounds having two or more isocyanate (NCO) groups permolecule. As used herein, aromatic aliphatic compounds should beunderstood as those containing an aromatic ring, wherein the isocyanategroup is not directly bonded to the ring. One example of an aromaticaliphatic compound is a tetramethylene diisocyanate (TMXDI). Theisocyanates may be organic polyisocyanate-terminated prepolymers, lowfree isocyanate prepolymer, and mixtures thereof. Theisocyanate-containing reactable component also may include anyisocyanate-functional monomer, dimer, trimer, or polymeric adductthereof, prepolymer, quasi-prepolymer, or mixtures thereof.Isocyanate-functional compounds may include monoisocyanates orpolyisocyanates that include any isocyanate functionality of two ormore.

Suitable isocyanate-containing components include diisocyanates havingthe generic structure: O═C═N—R—N═C═O, where R preferably is a cyclic,aromatic, or linear or branched hydrocarbon moiety containing from about1 to about 50 carbon atoms. The isocyanate also may contain one or morecyclic groups or one or more phenyl groups. When multiple cyclic oraromatic groups are present, linear and/or branched hydrocarbonscontaining from about 1 to about 10 carbon atoms can be present asspacers between the cyclic or aromatic groups. In some cases, the cyclicor aromatic group(s) may be substituted at the 2-, 3-, and/or4-positions, or at the ortho-, meta-, and/or para-positions,respectively. Substituted groups may include, but are not limited to,halogens, primary, secondary, or tertiary hydrocarbon groups, or amixture thereof.

Examples of isocyanates that can be used with the present inventioninclude, but are not limited to, substituted and isomeric mixturesincluding 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI);3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate(TDI); polymeric MDI; carbodiimide-modified liquid 4,4′-diphenylmethanediisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylenediisocyanate (MPDI); triphenyl methane-4,4′- and triphenylmethane-4,4″-triisocyanate; naphthylene-1,5-diisocyanate; 2,4′-, 4,4′-,and 2,2-biphenyl diisocyanate; polyphenylene polymethylenepolyisocyanate (PMDI) (also known as polymeric PMDI); mixtures of MDIand PMDI; mixtures of PMDI and TDI; ethylene diisocyanate;propylene-1,2-diisocyanate; trimethylene diisocyanate; butylenesdiisocyanate; bitolylene diisocyanate; tolidine diisocyanate;tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate;tetramethylene-1,4-diisocyanate; pentamethylenediisocyanate;1,6-hexamethylene diisocyanate (HDI); octamethylenediisocyanate; decamethylene diisocyanate; 2,2,4-trimethylhexamethylenediisocyanate; 2,4,4-trimethylhexamethylene diisocyanate;dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate;cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; diethylidenediisocyanate; methylcyclohexylene diisocyanate (HTDI);2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate;4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate;1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4′-bis(isocyanatomethyl) dicyclohexane;2,4′-bis(isocyanatomethyl) dicyclohexane; isophorone diisocyanate(IPDI); dimeryl diisocyanate, dodecane-1,12-diisocyanate,1,10-decamethylene diisocyanate, cyclohexylene-1,2-diisocyanate,1,10-decamethylene diisocyanate, 1-chlorobenzene-2,4-diisocyanate,furfurylidene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate,2,2,4-trimethyl hexamethylene diisocyanate, dodecamethylenediisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,3-cyclobutane diisocyanate, 1,4-cyclohexanediisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate),4,4′-methylenebis(phenyl isocyanate), 1-methyl-2,4-cyclohexanediisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanato-methyl)cyclohexane,1,6-diisocyanato-2,2,4,4-tetra-methylhexane,1,6-diisocyanato-2,4,4-tetra-trimethylhexane,trans-cyclohexane-1,4-diisocyanate,3-isocyanato-methyl-3,5,5-trimethylcyclo-hexyl isocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexylisocyanate, dicyclohexylmethane 4,4′-diisocyanate,1,4-bis(isocyanatomethyl) cyclohexane, m-phenylene diisocyanate,m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-phenylenediisocyanate, p,p′-biphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenylenediisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate,3,3′-diphenyl-4,4′-biphenylene diisocyanate, 4,4′-biphenylenediisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate,1,5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate,1,5-tetrahydronaphthalene diisocyanate, metaxylene diisocyanate,2,4-toluene diisocyanate, 2,4′-diphenylmethane diisocyanate,2,4-chlorophenylene diisocyanate, 4,4′-diphenylmethane diisocyanate,p,p′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, 2,2-diphenylpropane-4,4′-diisocyanate,4,4′-toluidine diisocyanate, dianidine diisocyanate, 4,4′-diphenyl etherdiisocyanate, 1, 3-xylylene diisocyanate, 1,4-naphthylene diisocyanate,azobenzene-4,4′-diisocyanate, diphenyl sulfone-4,4′-diisocyanate,triphenylmethane 4,4′,4″-triisocyanate, isocyanatoethyl methacrylate,3-isopropenyl-α,α-dimethylbenzyl-isocyanate, dichlorohexamethylenediisocyanate, ω′-diisocyanato-1,4-diethylbenzene, polymethylenepolyphenylene polyisocyanate, isocyanurate modified compounds, andcarbodiimide modified compounds, as well as biuret modified compounds ofthe above polyisocyanates. These isocyanates may be used either alone orin combination. These combination isocyanates include triisocyanates,such as biuret of hexamethylene diisocyanate and triphenylmethanetriisocyanates, and polyisocyanates, such as polymeric diphenylmethanediisocyanate.triisocyanate of HDI; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethanediisocyanate (H₁₂MDI); 2,4-hexahydrotoluene diisocyanate;2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3-, and 1,4-phenylenediisocyanate; aromatic aliphatic isocyanate, such as 1,2-, 1,3-, and1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI);para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurateof any polyisocyanate, such as isocyanurate of toluene diisocyanate,trimer of diphenylmethane diisocyanate, trimer of tetramethylxylenediisocyanate, isocyanurate of hexamethylene diisocyanate, and mixturesthereof, dimerized uretdione of any polyisocyanate, such as uretdione oftoluene diisocyanate, uretdione of hexamethylene diisocyanate, andmixtures thereof; modified polyisocyanate derived from the aboveisocyanates and polyisocyanates; and mixtures thereof.

In view of the advantages of injection molding versus the more complexcasting process, under some circumstances it is advantageous to haveformulations capable of curing as a thermoset but only within aspecified temperature range above that of the typical injection moldingprocess. This allows parts, such as golf ball cover layers, to beinitially injection molded, followed by subsequent processing at highertemperatures and pressures to induce further crosslinking and curing,resulting in thermoset properties in the final part. Such an initiallyinjection moldable composition is thus called a post curable urethane orurea composition.

If a post curable urethane composition is required, a modified orblocked diisocyanate which subsequently unblocks and induces furthercross linking post extrusion may be included in the diisocyanatestarting material. Modified isocyanates used for making thepolyurethanes of the present invention generally are defined as chemicalcompounds containing isocyanate groups that are not reactive at roomtemperature, but that become reactive once they reach a characteristictemperature. The resulting isocyanates can act as crosslinking agents orchain extenders to form crosslinked polyurethanes. The degree ofcrosslinking is governed by type and concentration of modifiedisocyanate presented in the composition. The modified isocyanate used inthe composition preferably is selected, in part, to have acharacteristic temperature sufficiently high such that the urethane inthe composition will retain its thermoplastic behavior during initialprocessing (such as injection molding). If a characteristic temperatureis too low, the composition crosslinks before processing is completed,leading to process difficulties. The modified isocyanate preferably isselected from isophorone diisocyanate (IPDI)-based uretdione-typecrosslinker; a combination of a uretdione adduct of IPDI and a partiallye-caprolactam-modified IPDI; a combination of isocyanate adductsmodified by e-caprolactam and a carboxylic acid functional group; acaprolactam-modified Desmodur diisocyanate; a Desmodur diisocyanatehaving a 3,5-dimethyl pyrazole modified isocyanate; or mixtures ofthese. Particular preferred examples of modified isocyanates includethose marketed under the trade name CRELAN by Bayer Corporation.Examples of these include: CRELAN TP LS 2147; CRELAN NI 2; isophoronediisocyanate (IPDI)-based uretdione-type crosslinker, such as CRELAN VPLS 2347; a combination of a uretdione adduct of IPDI and a partiallye-caprolactam-modified IPDI, such as CRELAN VP LS 2386; a combination ofisocyanate adducts modified by e-caprolactam and a carboxylic acidfunctional group, such as CRELAN VP LS 2181/1; a caprolactam-modifiedDesmodur diisocyanate, such as CRELAN NWS; and a Desmodur diisocyanatehaving a 3,5-dimethyl pyrazole modified isocyanate, such as CRELAN XP7180. These modified isocyanates may be used either alone or incombination. Such modified diisocyanates are described in more detail inU.S. Pat. No. 6,939,924, the entire contents of which are herebyincorporated by reference.

As an alternative if a post curable polyurethane or polyurea compositionis required, the diisocyanate may further comprise reaction product of anitroso compound and a diisocyanate or a polyisocyanate. The reactionproduct has a characteristic temperature at which it decomposesregenerating the nitroso compound and diisocyanate or polyisocyanate,which can, by judicious choice of the post processing temperature, inturn induce further crosslinking in the originally thermoplasticcomposition resulting in thermoset-like properties. Such nitrosocompounds are described in more detail in U.S. Pat. No. 7,037,985 B2,the entire contents of which are hereby incorporated by reference.

Any polyol now known or hereafter developed is suitable for useaccording to the invention. Polyols suitable for use in the presentinvention include, but are not limited to, polyester polyols, polyetherpolyols, polycarbonate polyols and polydiene polyols such aspolybutadiene polyols.

Polyester polyols are prepared by condensation or step-growthpolymerization utilizing diacids. Primary diacids for polyester polyolsare adipic acid and isomeric phthalic acids. Adipic acid is used formaterials requiring added flexibility, whereas phthalic anhydride isused for those requiring rigidity. Some examples of polyester polyolsinclude poly(ethylene adipate) (PEA), poly(diethylene adipate) (PDA),poly(propylene adipate) (PPA), poly(tetramethylene adipate) (PBA),poly(hexamethylene adipate) (PHA), poly(neopentylene adipate) (PNA),polyols composed of 3-methyl-1,5-pentanediol and adipic acid, randomcopolymer of PEA and PDA, random copolymer of PEA and PPA, randomcopolymer of PEA and PBA, random copolymer of PHA and PNA, caprolactonepolyol obtained by the ring-opening polymerization of ϵ-caprolactone,and polyol obtained by opening the ring of β-methyl-δ-valerolactone withethylene glycol can be used either alone or in a combination thereof.Additionally, polyester polyol may be composed of a copolymer of atleast one of the following acids and at least one of the followingglycols. The acids include terephthalic acid, isophthalic acid, phthalicanhydride, oxalic acid, malonic acid, succinic acid, pentanedioic acid,hexanedioic acid, octanedioic acid, nonanedioic acid, adipic acid,azelaic acid, sebacic acid, dodecanedioic acid, dimer acid (a mixture),ρ-hydroxybenzoate, trimellitic anhydride, ϵ-caprolactone, andβ-methyl-δ-valerolactone. The glycols includes ethylene glycol,propylene glycol, butylene glycol, pentylene glycol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, neopentylene glycol, polyethyleneglycol, polytetramethylene glycol, 1,4-cyclohexane dimethanol,pentaerythritol, and 3-methyl-1,5-pentanediol.

Polyether polyols are prepared by the ring-opening additionpolymerization of an alkylene oxide (e.g. ethylene oxide and propyleneoxide) with an initiator of a polyhydric alcohol (e.g. diethyleneglycol), which is an active hydride. Specifically, polypropylene glycol(PPG), polyethylene glycol (PEG) or propylene oxide-ethylene oxidecopolymer can be obtained. Polytetramethylene ether glycol (PTMG) isprepared by the ring-opening polymerization of tetrahydrofuran, producedby dehydration of 1,4-butanediol or hydrogenation of furan.Tetrahydrofuran can form a copolymer with alkylene oxide. Specifically,tetrahydrofuran-propylene oxide copolymer or tetrahydrofuran-ethyleneoxide copolymer can be formed. The polyether polyol may be used eitheralone or in a combination.

Polycarbonate polyol is obtained by the condensation of a known polyol(polyhydric alcohol) with phosgene, chloroformic acid ester, dialkylcarbonate or diallyl carbonate. Particularly preferred polycarbonatepolyols contain a polyol component using 1,6-hexanediol, 1,4-butanediol,1,3-butanediol, neopentylglycol or 1,5-pentanediol. Polycarbonatepolyols can be used either alone or in a combination with other polyols.

Polydiene polyols include liquid diene polymer containing hydroxylgroups having an average of at least 1.7 functional groups, and maycomprise diene polymers or diene copolymers having from about 4 to about12 carbon atoms, or a copolymer of such diene with addition topolymerizable α-olefin monomer having 2 to 2.2 carbon atoms. Specificexamples include butadiene homopolymer, isoprene homopolymer,butadiene-styrene copolymer, butadiene-isoprene copolymer,butadiene-acrylonitrile copolymer, butadiene-2-ethyl hexyl acrylatecopolymer, and butadiene-n-octadecyl acrylate copolymer. These liquiddiene polymers can be obtained, for example, by heating a conjugateddiene monomer in the presence of hydrogen peroxide in a liquid reactant.

Polybutadiene polyol includes liquid diene polymer containing hydroxylgroups having an average of at least 1.7 functional groups, and may becomposed of diene polymer or diene copolymer having 4 to 12 carbonatoms, or a copolymer of such diene with addition to polymerizableα-olefin monomer having 2 to 2.2 carbon atoms. Specific examples includebutadiene homopolymer, isoprene homopolymer, butadiene-styrenecopolymer, butadiene-isoprene copolymer, butadiene-acrylonitrilecopolymer, butadiene-2-ethyl hexyl acrylate copolymer, andbutadiene-n-octadecyl acrylate copolymer. These liquid diene polymerscan be obtained, for example, by heating a conjugated diene monomer inthe presence of hydrogen peroxide in a liquid reactant

Any polyamine available to one of ordinary skill in the polyurethane artis suitable for use according to the disclosure herein. Polyaminessuitable for use include, but are not limited to, amine-terminatedcompounds typically are selected from amine-terminated hydrocarbons,amine-terminated polyethers, amine-terminated polyesters,amine-terminated polycaprolactones, amine-terminated polycarbonates,amine-terminated polyamides, and mixtures thereof. The amine-terminatedcompound may be a polyether amine selected from polytetramethylene etherdiamines, polyoxypropylene diamines, poly(ethylene oxide cappedoxypropylene) ether diamines, triethyleneglycoldiamines, propyleneoxide-based triamines, trimethylolpropane-based triamines,glycerin-based triamines, and mixtures thereof.

Diisocyanate and polyol or polyamine components may be combined to forma prepolymer prior to reaction with a chain extender or curing agent.Any such prepolymer combination is suitable for use in the presentinvention. Commercially available prepolymers include LFH580, LFH120,LFH710, LFH1570, LF930A, LF950A, LF601D, LF751D, LFG963A, LFG640D.

One preferred prepolymer is a toluene diisocyanate prepolymer withpolypropylene glycol. Such polypropylene glycol terminated toluenediisocyanate prepolymers are available from Uniroyal Chemical Company ofMiddlebury, Conn., under the trade name ADIPRENE® LFG963A and LFG640D.Most preferred prepolymers are the polytetramethylene ether glycolterminated toluene diisocyanate prepolymers including those availablefrom Uniroyal Chemical Company of Middlebury, Conn., under the tradename ADIPRENE® LF930A, LF950A, LF601D, and LF751D.

In one embodiment, the number of free NCO groups in the urethane or ureaprepolymer may be less than about 14 percent. Preferably the urethane orurea prepolymer has from about 3 percent to about 11 percent, morepreferably from about 4 to about 9.5 percent, and even more preferablyfrom about 3 percent to about 9 percent, free NCO on an equivalentweight basis.

Polyol chain extenders or curing agents may be primary, secondary, ortertiary polyols. Non-limiting examples of monomers of these polyolsinclude: trimethylolpropane (TMP), ethylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol,dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,1,2-pentanediol, 2,3-pentanediol, 2,5-hexanediol, 2,4-hexanediol,2-ethyl-1,3-hexanediol, cyclohexanediol, and2-ethyl-2-(hydroxymethyl)-1,3-propanediol.

Diamines and other suitable polyamines may be added to the compositionsto function as chain extenders or curing agents. These include primary,secondary and tertiary amines having two or more amines as functionalgroups. Exemplary diamines include aliphatic diamines, such astetramethylenediamine, pentamethylenediamine, hexamethylenediamine;alicyclic diamines, such as 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane; or aromatic diamines, such asdiethyl-2,4-toluenediamine,4,4″-methylenebis-(3-chloro,2,6-diethyl)-aniline(available from Air Products and Chemicals Inc., of Allentown, Pa.,under the trade name LONZACURE®), 3,3′-dichlorobenzidene;3,3′-dichloro-4,4′-diaminodiphenyl methane (MOCA);N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine,3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; N,N′-dialkyldiamino diphenylmethane; trimethylene-glycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate, 4,4′-methylenebis-2-chloroaniline, 2,2′,3,3′-tetrachloro-4,4′-diamino-phenyl methane,p,p′-methylenedianiline, p-phenylenediamine or 4,4′-diaminodiphenyl; and2,4,6-tris(dimethylaminomethyl) phenol.

Further examples include ethylene diamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicyclohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis-(methylamine);1,3-cyclohexane-bis-(methylamine); diethylene glycol bis-(aminopropyl)ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylene tetramine; tetraethylene pentamine; propylenediamine; 1,3-diaminopropane; dimethylamino propylamine; diethylaminopropylamine; imido-(bis-propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; and mixtures thereof.

Aromatic diamines have a tendency to provide a stiffer (i.e., having ahigher Mooney viscosity) product than aliphatic or cycloaliphaticdiamines

Depending on their chemical structure, curing agents may be slow- orfast-reacting polyamines or polyols. As described in U.S. Pat. Nos.6,793,864, 6,719,646 and copending U.S. Patent Publication No.2004/0201133 A1, (the contents of all of which are hereby incorporatedherein by reference), slow-reacting polyamines are diamines having aminegroups that are sterically and/or electronically hindered by electronwithdrawing groups or bulky groups situated proximate to the aminereaction sites. The spacing of the amine reaction sites will also affectthe reactivity speed of the polyamines.

Suitable curatives for use in the present invention are selected fromthe slow-reacting polyamine group include, but are not limited to,3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; N,N′-dialkyldiamino diphenylmethane; trimethylene-glycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate, and mixtures thereof. Ofthese, 3,5-dimethylthio-2,4-toluenediamine and3,5-dimethylthio-2,6-toluenediamine are isomers and are sold under thetrade name ETHACURE® 300 by Ethyl Corporation. Trimethyleneglycol-di-p-aminobenzoate is sold under the trade name POLACURE 740M andpolytetramethyleneoxide-di-p-aminobenzoates are sold under the tradename POLAMINES by Polaroid Corporation. N,N′-dialkyldiamino diphenylmethane is sold under the trade name UNILINK® by UOP.

When slow-reacting polyamines are used as the curing agent to produceurethane elastomers, a catalyst is typically needed to promote thereaction between the urethane prepolymer and the curing agent. Specificsuitable catalysts include TEDA (1) dissolved in di-propylene glycol(such as TEDA L33 available from Witco Corp. Greenwich, Conn., and DABCO33 LV available from Air Products and Chemicals Inc.). Catalysts areadded at suitable effective amounts, such as from about 2% to about 5%,and (2) more preferably TEDA dissolved in 1,4-butane diol from about 2%to about 5%. Another suitable catalyst includes a blend of 0.5% 33LV orTEDA L33 (above) with 0.1% dibutyl tin dilaurate (available from WitcoCorp. or Air Products and Chemicals, Inc.) which is added to a curativesuch as VIBRACURE® A250. Unfortunately, as is well known in the art, theuse of a catalyst can have a significant effect on the ability tocontrol the reaction and thus, on the overall processability.

To eliminate the need for a catalyst, a fast-reacting curing agent, oragents, can be used that does not have electron withdrawing groups orbulky groups that interfere with the reaction groups. However, theproblem with lack of control associated with the use of catalysts is notcompletely eliminated since fast-reacting curing agents also arerelatively difficult to control.

Preferred curing agent blends include using dicyandiamide in combinationwith fast curing agents such as diethyl-2,4-toluenediamine,4,4″-methylenebis-(3-chloro,2,6-diethyl)-aniline (available from AirProducts and Chemicals Inc., of Allentown, Pa., under the trade nameLONZACURE®), 3,3′-dichlorobenzidene; 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA); N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine andCuralon L, a trade name for a mixture of aromatic diamines sold byUniroyal, Inc. or any and all combinations thereof. A preferredfast-reacting curing agent is diethyl-2,4-toluene diamine, which has twocommercial grades names, Ethacure® 100 and Ethacure® 100LC commercialgrade has lower color and less by-product. In other words, it isconsidered a cleaner product to those skilled in the art.

Advantageously, the use of the Ethacure® 100LC commercial grade resultsin a golf ball that is less susceptible to yellowing when exposed to UVlight conditions. A player appreciates this desirable aesthetic effectalthough it should be noted that the instant invention may use either ofthese two commercial grades for the curing agentdiethyl-2,4-toluenediamine

If a reduced-yellowing post curable composition is required the chainextender or curing agent can further comprise a peroxide or peroxidemixture. Before the composition is exposed to sufficient thermal energyto reach the activation temperature of the peroxide, the composition of(a) and (b) behaves as a thermoplastic material. Therefore, it canreadily be formed into golf ball layers using injection molding.However, when sufficient thermal energy is applied to bring thecomposition above the peroxide activation temperature, crosslinkingoccurs, and the thermoplastic polyurethane is converted into crosslinkedpolyurethane.

Examples of suitable peroxides for use in compositions within the scopeof the present invention include aliphatic peroxides, aromaticperoxides, cyclic peroxides, or mixtures of these. Primary, secondary,or tertiary peroxides can be used, with tertiary peroxides mostpreferred. Also, peroxides containing more than one peroxy group can beused, such as 2,5-bis-(tert-butylperoxy)-2,5-dimethyl hexane and1,4-bis-(tert-butylperoxy-isopropyl)-benzene. Also, peroxides that areeither symmetrical or asymmetric can be used, such astert-butylperbenzoate and tert-butylcumylperoxide. Additionally,peroxides having carboxy groups also can be used. Decomposition ofperoxides used in compositions within the scope of the present inventioncan be brought about by applying thermal energy, shear, reactions withother chemical ingredients, or a combination of these. Homolyticallydecomposed peroxide, heterolytically decomposed peroxide, or a mixtureof those can be used to promote crosslinking reactions in compositionswithin the scope of this invention. Examples of suitable aliphaticperoxides and aromatic peroxides include diacetylperoxide,di-tert-butylperoxide, dibenzoylperoxide, dicumylperoxide,2,5-bis-(t-butylperoxy)-2,5-dimethyl hexane,2,5-dimethyl-2,5-di(benzoylperoxy)hexane,2,5-dimethyl-2,5-di(butylperoxy)-3-hexyne,n-butyl-4,4-bis(t-butylperoxyl) valerate,1,4-bis-(t-butylperoxyisopropyl)-benzene, t-butyl peroxybenzoate,1,1-bis-(t-butylperoxy)-3,3,5 tri-methylcyclohexane, anddi(2,4-dichloro-benzoyl). Peroxides for use within the scope of thisinvention may be acquired from Akzo Nobel Polymer Chemicals of Chicago,Ill., Atofina of Philadelphia, Pa. and Akrochem of Akron, Ohio. Furtherdetails of this post curable system are disclosed in U.S. Pat. No.6,924,337, the entire contents of which are hereby incorporated byreference.

The core, cover layer and, optionally, one or more inner cover layers ofthe golf ball may further comprise one or more ionomer resins. Onefamily of such resins was developed in the mid-1960's, by E.I. DuPont deNemours and Co., and sold under the trademark SURLYN®. Preparation ofsuch ionomers is well known, for example see U.S. Pat. No. 3,264,272.Generally speaking, most commercial ionomers are unimodal and consist ofa polymer of a mono-olefin, e.g., an alkene, with an unsaturated mono-or dicarboxylic acids having 3 to 12 carbon atoms. An additional monomerin the form of a mono- or dicarboxylic acid ester may also beincorporated in the formulation as a so-called “softening comonomer”.The incorporated carboxylic acid groups are then neutralized by a basicmetal ion salt, to form the ionomer. The metal cations of the basicmetal ion salt used for neutralization include Li⁺, Na⁺, K⁺, Zn²⁺, Ca²⁺,Co²⁺, Ni²⁺, Cu²⁺, Pb²⁺, and Mg²⁺, with the Li⁺, Na⁺, Ca²⁺, Zn²⁺, andMg²⁺ being preferred. The basic metal ion salts include those of forexample formic acid, acetic acid, nitric acid, and carbonic acid,hydrogen carbonate salts, oxides, hydroxides, and alkoxides.

The first commercially available ionomer resins contained up to 16weight percent acrylic or methacrylic acid, although it was also wellknown at that time that, as a general rule, the hardness of these covermaterials could be increased with increasing acid content. Hence, inResearch Disclosure 29703, published in January 1989, DuPont disclosedionomers based on ethylene/acrylic acid or ethylene/methacrylic acidcontaining acid contents of greater than 15 weight percent. In this samedisclosure, DuPont also taught that such so called “high acid ionomers”had significantly improved stiffness and hardness and thus could beadvantageously used in golf ball construction, when used either singlyor in a blend with other ionomers.

More recently, high acid ionomers can be ionomer resins with acrylic ormethacrylic acid units present from 16 wt. % to about 35 wt. % in thepolymer. Generally, such a high acid ionomer will have a flexuralmodulus from about 50,000 psi to about 125,000 psi.

Ionomer resins further comprising a softening comonomer, present fromabout 10 wt. % to about 50 wt. % in the polymer, have a flexural modulusfrom about 2,000 psi to about 10,000 psi, and are sometimes referred toas “soft” or “very low modulus” ionomers. Typical softening comonomersinclude n-butyl acrylate, iso-butyl acrylate, n-butyl methacrylate,methyl acrylate and methyl methacrylate.

Today, there are a wide variety of commercially available ionomer resinsbased both on copolymers of ethylene and (meth)acrylic acid orterpolymers of ethylene and (meth)acrylic acid and (meth)acrylate, allof which can be used as a golf ball component. The properties of theseionomer resins can vary widely due to variations in acid content,softening comonomer content, the degree of neutralization, and the typeof metal ion used in the neutralization. The full range commerciallyavailable typically includes ionomers of polymers of general formula,E/X/Y polymer, wherein E is ethylene, X is a C₃ to C₈ α,β ethylenicallyunsaturated carboxylic acid, such as acrylic or methacrylic acid, and ispresent in an amount from about 0 wt. % to about 50 wt. %, particularlyabout 2 to about 30 weight %, of the E/X/Y copolymer, and Y is asoftening comonomer selected from the group consisting of alkyl acrylateand alkyl methacrylate, such as methyl acrylate or methyl methacrylate,and wherein the alkyl groups have from 1-8 carbon atoms, Y is in therange of 0 to about 50 weight %, particularly about 5 wt. % to about 35wt. %, of the E/X/Y copolymer, and wherein the acid groups present insaid ionomeric polymer are partially (e.g., about 1% to about 90%)neutralized with a metal selected from the group consisting of lithium,sodium, potassium, magnesium, calcium, barium, lead, tin, zinc oraluminum, or a combination of such cations.

The ionomer may also be a so-called bimodal ionomer as described in U.S.Pat. No. 6,562,906 (the entire contents of which are herein incorporatedby reference). These ionomers are bimodal as they are prepared fromblends comprising polymers of different molecular weights. Specificallythey include bimodal polymer blend compositions comprising:

-   -   a) a high molecular weight component having weight average        molecular weight (M_(W)) of about 80,000 to about 500,000 and        comprising one or more ethylene/α, β-ethylenically unsaturated        C₃₋₈ carboxylic acid copolymers and/or one or more ethylene,        alkyl (meth)acrylate, (meth)acrylic acid terpolymers; said high        molecular weight component being partially neutralized with        metal ions selected from the group consisting of lithium,        sodium, zinc, calcium, magnesium, and a mixture of any these;        and    -   b) a low molecular weight component having a weight average        molecular weight (M_(W)) of about from about 2,000 to about        30,000 and comprising one or more ethylene/α, β-ethylenically        unsaturated C₃₋₈ carboxylic acid copolymers and/or one or more        ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers;        said low molecular weight component being partially neutralized        with metal ions selected from the group consisting of lithium,        sodium, zinc, calcium, magnesium, and a mixture of any these.

In addition to the unimodal and bimodal ionomers, also included are theso-called “modified ionomers” examples of which are described in U.S.Pat. Nos. 6,100,321, 6,329,458 and 6,616,552 and U.S. Patent PublicationNo. US 2003/0158312 A1, the entire contents of all of which are hereinincorporated by reference.

The modified unimodal ionomers may be prepared by mixing:

-   -   a) an ionomeric polymer comprising ethylene, from 5 to 25 weight        percent (meth)acrylic acid, and from 0 to 40 weight percent of a        (meth)acrylate monomer, said ionomeric polymer neutralized with        metal ions selected from the group consisting of lithium,        sodium, zinc, calcium, magnesium, and a mixture of any of these;        and    -   b) from about 5 to about 40 weight percent (based on the total        weight of said modified ionomeric polymer) of one or more fatty        acids or metal salts of said fatty acid, the metal selected from        the group consisting of calcium, sodium, zinc, potassium, and        lithium, barium and magnesium and the fatty acid preferably        being stearic acid.

The modified bimodal ionomers, which are ionomers derived from theearlier described bimodal ethylene/carboxylic acid polymers (asdescribed in U.S. Pat. No. 6,562,906, the entire contents of which areherein incorporated by reference), are prepared by mixing;

-   -   a) a high molecular weight component having weight average        molecular weight (M_(W)) of about 80,000 to about 500,000 and        comprising one or more ethylene/α, β-ethylenically unsaturated        C₃₋₈ carboxylic acid copolymers and/or one or more ethylene,        alkyl (meth)acrylate, (meth)acrylic acid terpolymers; said high        molecular weight component being partially neutralized with        metal ions selected from the group consisting of lithium,        sodium, zinc, calcium, potassium, magnesium, and a mixture of        any of these; and    -   b) a low molecular weight component having a weight average        molecular weight (M_(W)) of about from about 2,000 to about        30,000 and comprising one or more ethylene/α, β-ethylenically        unsaturated C₃₋₈ carboxylic acid copolymers and/or one or more        ethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers;        said low molecular weight component being partially neutralized        with metal ions selected from the group consisting of lithium,        sodium, zinc, calcium, potassium, magnesium, and a mixture of        any of these; and    -   c) from about 5 to about 40 weight percent (based on the total        weight of said modified ionomeric polymer) of one or more fatty        acids or metal salts of said fatty acid, the metal selected from        the group consisting of calcium, sodium, zinc, potassium and        lithium, barium and magnesium and the fatty acid preferably        being stearic acid.

The fatty or waxy acid salts utilized in the various modified ionomersare composed of a chain of alkyl groups containing from about 4 to 75carbon atoms (usually even numbered) and characterized by a —COOHterminal group. The generic formula for all fatty and waxy acids aboveacetic acid is CH₃ (CH₂)_(X) COOH, wherein the carbon atom countincludes the carboxyl group. The fatty or waxy acids utilized to producethe fatty or waxy acid salts modifiers may be saturated or unsaturated,and they may be present in solid, semi-solid or liquid form.

Examples of suitable saturated fatty acids, i.e., fatty acids in whichthe carbon atoms of the alkyl chain are connected by single bonds,include but are not limited to stearic acid (C₁₈, i.e., CH₃ (CH₂)₁₆COOH), palmitic acid (C₁₆, i.e., CH₃ (CH₂)₁₄ COOH), pelargonic acid (C₉,i.e., CH₃ (CH₂)₇ COOH) and lauric acid (Cu, i.e., CH₃ (CH₂)₁₀ OCOOH).Examples of suitable unsaturated fatty acids, i.e., a fatty acid inwhich there are one or more double bonds between the carbon atoms in thealkyl chain, include but are not limited to oleic acid (C₁₃, i.e., CH₃(CH₂)₇ CH:CH(CH₂)₇ COOH).

The source of the metal ions used to produce the metal salts of thefatty or waxy acid salts used in the various modified ionomers aregenerally various metal salts which provide the metal ions capable ofneutralizing, to various extents, the carboxylic acid groups of thefatty acids. These include the sulfate, carbonate, acetate andhydroxylate salts of zinc, barium, calcium and magnesium.

Since the fatty acid salts modifiers comprise various combinations offatty acids neutralized with a large number of different metal ions,several different types of fatty acid salts may be utilized in theinvention, including metal stearates, laureates, oleates, andpalmitates, with calcium, zinc, sodium, lithium, potassium and magnesiumstearate being preferred, and calcium and sodium stearate being mostpreferred.

The fatty or waxy acid or metal salt of said fatty or waxy acid ispresent in the modified ionomeric polymers in an amount of from about 5to about 40, preferably from about 7 to about 35, more preferably fromabout 8 to about 20 weight percent (based on the total weight of saidmodified ionomeric polymer).

As a result of the addition of the one or more metal salts of a fatty orwaxy acid, from about 40 to 100, preferably from about 50 to 100, morepreferably from about 70 to 100 percent of the acidic groups in thefinal modified ionomeric polymer composition are neutralized by a metalion.

An example of such a modified ionomer polymer is DuPont® HPF-1000available from E.I. DuPont de Nemours and Co. Inc.

A preferred ionomer composition may be prepared by blending one or moreof the unimodal ionomers, bimodal ionomers, or modified unimodal orbimodal ionomeric polymers as described herein, and further blended witha zinc neutralized ionomer of a polymer of general formula E/X/Y where Eis ethylene, X is a softening comonomer such as acrylate or methacrylateand is present in an amount of from 0 to about 50, preferably 0 to about25, most preferably 0, and Y is acrylic or methacrylic acid and ispresent in an amount from about 5 wt. % to about 25, preferably fromabout 10 to about 25, and most preferably about 10 to about 20 wt. % ofthe total composition.

In particular embodiment, blends used to make the core, intermediateand/or cover layers may include about 5 to about 95 wt. %, particularlyabout 5 to about 75 wt. %, preferably about 5 to about 55 wt. %, of aspecialty propylene elastomer(s) and about 95 to about 5 wt. %,particularly about 95 to about 25 wt. %, preferably about 95 to about 45wt. %, of at least one ionomer, especially a high-acid ionomer.

In yet another embodiment, a blend of an ionomer and a block copolymercan be included in the composition. An example of a block copolymer is afunctionalized styrenic block copolymer, the block copolymerincorporating a first polymer block having an aromatic vinyl compound, asecond polymer block having a conjugated diene compound, and a hydroxylgroup located at a block copolymer, or its hydrogenation product, inwhich the ratio of block copolymer to ionomer ranges from 5:95 to 95:5by weight, more preferably from about 10:90 to about 90:10 by weight,more preferably from about 20:80 to about 80:20 by weight, morepreferably from about 30:70 to about 70:30 by weight and most preferablyfrom about 35:65 to about 65:35 by weight. A preferred block copolymeris SEPTON HG-252. Such blends are described in more detail incommonly-assigned U.S. Pat. No 6,861,474 and U.S. Patent Publication No.2003/0224871 both of which are incorporated herein by reference in theirentireties.

In a further embodiment, the core, mantle and/or cover layers (andparticularly a mantle layer) can comprise a composition prepared byblending together at least three materials, identified as Components A,B, and C, and melt-processing these components to form in-situ a polymerblend composition incorporating a pseudo-crosslinked polymer network.Such blends are described in more detail in commonly-assigned U.S. Pat.No. 6,930,150, which is incorporated by reference herein in itsentirety. Component A is a monomer, oligomer, prepolymer or polymer thatincorporates at least five percent by weight of at least one type of ananionic functional group, and more preferably between about 5% and 50%by weight. Component B is a monomer, oligomer, or polymer thatincorporates less by weight of anionic functional groups than doesComponent A, Component B preferably incorporates less than about 25% byweight of anionic functional groups, more preferably less than about 20%by weight, more preferably less than about 10% by weight, and mostpreferably Component B is free of anionic functional groups. Component Cincorporates a metal cation, preferably as a metal salt. Thepseudo-crosslinked network structure is formed in-situ, not by covalentbonds, but instead by ionic clustering of the reacted functional groupsof Component A. The method can incorporate blending together more thanone of any of Components A, B, or C.

The polymer blend can include either Component A or B dispersed in aphase of the other. Preferably, blend compositions comprises betweenabout 1% and about 99% by weight of Component A based on the combinedweight of Components A and B, more preferably between about 10% andabout 90%, more preferably between about 20% and about 80%, and mostpreferably, between about 30% and about 70%. Component C is present in aquantity sufficient to produce the preferred amount of reaction of theanionic functional groups of Component A after sufficientmelt-processing. Preferably, after melt-processing at least about 5% ofthe anionic functional groups in the chemical structure of Component Ahave been consumed, more preferably between about 10% and about 90%,more preferably between about 10% and about 80%, and most preferablybetween about 10% and about 70%.

The composition preferably is prepared by mixing the above materialsinto each other thoroughly, either by using a dispersive mixingmechanism, a distributive mixing mechanism, or a combination of these.These mixing methods are well known in the manufacture of polymerblends. As a result of this mixing, the anionic functional group ofComponent A is dispersed evenly throughout the mixture. Next, reactionis made to take place in-situ at the site of the anionic functionalgroups of Component A with Component C in the presence of Component B.This reaction is prompted by addition of heat to the mixture. Thereaction results in the formation of ionic clusters in Component A andformation of a pseudo-crosslinked structure of Component A in thepresence of Component B. Depending upon the structure of Component B,this pseudo-crosslinked Component A can combine with Component B to forma variety of interpenetrating network structures. For example, thematerials can form a pseudo-crosslinked network of Component A dispersedin the phase of Component B, or Component B can be dispersed in thephase of the pseudo-crosslinked network of Component A. Component B mayor may not also form a network, depending upon its structure, resultingin either: a fully-interpenetrating network, i.e., two independentnetworks of Components A and B penetrating each other, but notcovalently bonded to each other; or, a semi-interpenetrating network ofComponents A and B, in which Component B forms a linear, grafted, orbranched polymer interspersed in the network of Component A. Forexample, a reactive functional group or an unsaturation in Component Bcan be reacted to form a crosslinked structure in the presence of thein-situ-formed, pseudo-crosslinked structure of Component A, leading toformation of a fully-interpenetrating network. Any anionic functionalgroups in Component B also can be reacted with the metal cation ofComponent C, resulting in pseudo-crosslinking via ionic clusterattraction of Component A to Component B.

The level of in-situ-formed pseudo-crosslinking in the compositionsformed by the present methods can be controlled as desired by selectionand ratio of Components A and B, amount and type of anionic functionalgroup, amount and type of metal cation in Component C, type and degreeof chemical reaction in Component B, and degree of pseudo-crosslinkingproduced of Components A and B.

As discussed above, the mechanical and thermal properties of the polymerblend for the inner mantle layer and/or the outer mantle layer can becontrolled as required by a modifying any of a number of factors,including: chemical structure of Components A and B, particularly theamount and type of anionic functional groups; mean molecular weight andmolecular weight distribution of Components A and B; linearity andcrystallinity of Components A and B; type of metal cation in ComponentC; degree of reaction achieved between the anionic functional groups andthe metal cation; mix ratio of Component A to Component B; type anddegree of chemical reaction in Component B; presence of chemicalreaction, such as a crosslinking reaction, between Components A and B;and the particular mixing methods and conditions used.

As discussed above, Component A can be any monomer, oligomer,prepolymer, or polymer incorporating at least 5% by weight of anionicfunctional groups. Those anionic functional groups can be incorporatedinto monomeric, oligomeric, prepolymeric, or polymeric structures duringthe synthesis of Component A, or they can be incorporated into apre-existing monomer, oligomer, prepolymer, or polymer throughsulfonation, phosphonation, or carboxylation to produce Component A.

Preferred, but non-limiting, examples of suitable copolymers andterpolymers include copolymers or terpolymers of: ethylene/acrylic acid,ethylene/methacrylic acid, ethylene/itaconic acid, ethylene/methylhydrogen maleate, ethylene/maleic acid, ethylene/methacrylicacid/ethylacrylate, ethylene/itaconic acid/methyl methacrylate,ethylene/methyl hydrogen maleate/ethyl acrylate, ethylene/methacrylicacid/vinyl acetate, ethylene/acrylic acid/vinyl alcohol,ethylene/propylene/acrylic acid, ethylene/styrene/acrylic acid,ethylene/methacrylic acid/acrylonitrile, ethylene/fumaric acid/vinylmethyl ether, ethylene/vinyl chloride/acrylic acid, ethylene/vinyldienechloride/acrylic acid, ethylene/vinyl fluoride/methacrylic acid, andethylene/chlorotrifluoroethylene/methacrylic acid, or anymetallocene-catalyzed polymers of the above-listed species.

Another family of thermoplastic elastomers for use in the golf balls arepolymers of i) ethylene and/or an alpha olefin; and ii) an α,β-ethylenically unsaturated C₃-C₂₀ carboxylic acid or anhydride, or anα, β-ethylenically unsaturated C₃-C₂₀ sulfonic acid or anhydride or anα, β-ethylenically unsaturated C₃-C₂₀ phosphoric acid or anhydride and,optionally iii) a C₁-C₁₀ ester of an α, β-ethylenically unsaturatedC₃-C₂₀ carboxylic acid or a C₁-C₁₀ ester of an α, β-ethylenicallyunsaturated C₃-C₂₀ sulfonic acid or a C₁-C₁₀ ester of an α,β-ethylenically unsaturated C₃-C₂₀ phosphoric acid.

Preferably, the alpha-olefin has from 2 to 10 carbon atoms and ispreferably ethylene, and the unsaturated carboxylic acid is a carboxylicacid having from about 3 to 8 carbons. Examples of such acids includeacrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid,crotonic acid, maleic acid, fumaric acid, and itaconic acid, withacrylic acid being preferred. Preferably, the carboxylic acid ester ifpresent may be selected from the group consisting of vinyl esters ofaliphatic carboxylic acids wherein the acids have 2 to 10 carbon atomsand vinyl ethers wherein the alkyl groups contain 1 to 10 carbon atoms.

Examples of such polymers suitable for use include, but are not limitedto, an ethylene/acrylic acid copolymer, an ethylene/methacrylic acidcopolymer, an ethylene/itaconic acid copolymer, an ethylene/maleic acidcopolymer, an ethylene/methacrylic acid/vinyl acetate copolymer, anethylene/acrylic acid/vinyl alcohol copolymer, and the like.

Most preferred are ethylene/(meth)acrylic acid copolymers andethylene/(meth)acrylic acid/alkyl (meth)acrylate terpolymers, orethylene and/or propylene maleic anhydride copolymers and terpolymers.

The acid content of the polymer may contain anywhere from 1 to 30percent by weight acid. In some instances, it is preferable to utilize ahigh acid copolymer (i.e., a copolymer containing greater than 16% byweight acid, preferably from about 17 to about 25 weight percent acid,and more preferably about 20 weight percent acid).

Examples of such polymers which are commercially available include, butare not limited to, the Escor® 5000, 5001, 5020, 5050, 5070, 5100, 5110and 5200 series of ethylene-acrylic acid copolymers sold by Exxon andthe PRIMACOR® 1321, 1410, 1410-XT, 1420, 1430, 2912, 3150, 3330, 3340,3440, 3460, 4311, 4608 and 5980 series of ethylene-acrylic acidcopolymers sold by The Dow Chemical Company, Midland, Mich.

Also included are the bimodal ethylene/carboxylic acid polymers asdescribed in U.S. Pat. No. 6,562,906. These polymers compriseethylene/α, β-ethylenically unsaturated C₃₋₈ carboxylic acid highcopolymers, particularly ethylene (meth)acrylic acid copolymers andethylene, alkyl (meth)acrylate, (meth)acrylic acid terpolymers, havingmolecular weights of about 80,000 to about 500,000 which are meltblended with ethylene/α, β-ethylenically unsaturated C₃₋₈ carboxylicacid copolymers, particularly ethylene/(meth)acrylic acid copolymershaving molecular weights of about 2,000 to about 30,000.

As discussed above, Component B can be any monomer, oligomer, orpolymer, preferably having a lower weight percentage of anionicfunctional groups than that present in Component A in the weight rangesdiscussed above, and most preferably free of such functional groups.Examples of suitable materials for Component B include, but are notlimited to, the following: thermoplastic elastomer, thermoset elastomer,synthetic rubber, thermoplastic vulcanizate, copolymeric ionomer,terpolymeric ionomer, polycarbonate, polyolefin, polyamide, copolymericpolyamide, polyesters, polyvinyl alcohols,acrylonitrile-butadiene-styrene copolymers, polyurethane, polyarylate,polyacrylate, polyphenyl ether, modified-polyphenyl ether, high-impactpolystyrene, diallyl phthalate polymer, metallocene catalyzed polymers,acrylonitrile-styrene-butadiene (ABS), styrene-acrylonitrile (SAN)(including olefin-modified SAN and acrilonitrile styrene acrylonitrile),styrene-maleic anhydryde (S/MA) polymer, styrenic copolymer,functionalized styrenic copolymer, functionalized styrenic terpolymer,styrenic terpolymer, cellulose polymer, liquid crystal polymer (LCP),ethylene-propylene-diene terpolymer (EPDM), ethylene-propylenecopolymer, ethylene vinyl acetate, polyurea, and polysiloxane or anymetallocene-catalyzed polymers of these species. Particularly suitablepolymers for use as Component B include polyethylene-terephthalate,polybutyleneterephthalate, polytrimethylene-terephthalate,ethylene-carbon monoxide copolymer, polyvinyl-diene fluorides,polyphenylenesulfide, polypropyleneoxide, polyphenyloxide,polypropylene, functionalized polypropylene, polyethylene,ethylene-octene copolymer, ethylene-methyl acrylate, ethylene-butylacrylate, polycarbonate, polysiloxane, functionalized polysiloxane,copolymeric ionomer, terpolymeric ionomer, polyetherester elastomer,polyesterester elastomer, polyetheramide elastomer, propylene-butadienecopolymer, modified copolymer of ethylene and propylene, styreniccopolymer (including styrenic block copolymer and randomly distributedstyrenic copolymer, such as styrene-isobutylene copolymer andstyrene-butadiene copolymer), partially or fully hydrogenatedstyrene-butadiene-styrene block copolymers such asstyrene-(ethylene-propylene)-styrene orstyrene-(ethylene-butylene)-styrene block copolymers, partially or fullyhydrogenated styrene-butadiene-styrene block copolymers with functionalgroup, polymers based on ethylene-propylene-(diene), polymers based onfunctionalized ethylene-propylene-diene), dynamically vulcanizedpolypropylene/ethylene-propylene-diene-copolymer, thermoplasticvulcanizates based on ethylene-propylene-(diene), thermoplasticpolyetherurethane, thermoplastic polyesterurethane, compositions formaking thermoset polyurethane, thermoset polyurethane, natural rubber,styrene-butadiene rubber, nitrile rubber, chloroprene rubber,fluorocarbon rubber, butyl rubber, acrylic rubber, silicone rubber,chlorosulfonated polyethylene, polyisobutylene, alfin rubber, polyesterrubber, epichlorohydrin rubber, chlorinated isobutylene-isoprene rubber,nitrile-isobutylene rubber, 1,2-polybutadiene, 1,4-polybutadiene,cis-polyisoprene, trans-polyisoprene, and polybutylene-octene.

Preferred materials for use as Component B include polyester elastomersmarketed under the name PEBAX and LOTADER marketed by ATOFINA Chemicalsof Philadelphia, Pa.; HYTREL, FUSABOND, and NUCREL marketed by E.I.DuPont de Nemours & Co. of Wilmington, Del.; SKYPEL and SKYTHANE by S.K.Chemicals of Seoul, South Korea; SEPTON and HYBRAR marketed by KurarayCompany of Kurashiki, Japan; ESTHANE by Noveon; and KRATON marketed byKraton Polymers. A most preferred material for use as Component B isSEPTON HG-252.

As stated above, Component C is a metal cation. These metals are fromgroups IA, IB, IIA, IIB, MA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB andVIIIB of the periodic table. Examples of these metals include lithium,sodium, magnesium, aluminum, potassium, calcium, manganese, tungsten,titanium, iron, cobalt, nickel, hafnium, copper, zinc, barium,zirconium, and tin. Suitable metal compounds for use as a source ofComponent C are, for example, metal salts, preferably metal hydroxides,metal carbonates, or metal acetates. In addition to Components A, B, andC, other materials commonly used in polymer blend compositions, can beincorporated into compositions prepared using these methods, including:crosslinking agents, co-crosslinking agents, accelerators, activators,UV-active chemicals such as UV initiators, EB-active chemicals,colorants, UV stabilizers, optical brighteners, antioxidants, processingaids, mold release agents, foaming agents, and organic, inorganic ormetallic fillers or fibers, including fillers to adjust specificgravity.

Various known methods are suitable for preparation of polymer blends.For example, the three components can be premixed together in any typeof suitable mixer, such as a V-blender, tumbler mixer, or blade mixer.This premix then can be melt-processed using an internal mixer, such asBanbury mixer, roll-mill or combination of these, to produce a reactionproduct of the anionic functional groups of Component A by Component Cin the presence of Component B. Alternatively, the premix can bemelt-processed using an extruder, such as single screw, co-rotating twinscrew, or counter-rotating twin screw extruder, to produce the reactionproduct. The mixing methods discussed above can be used together tomelt-mix the three components to prepare the compositions of the presentinvention. Also, the components can be fed into an extrudersimultaneously or sequentially.

Most preferably, Components A and B are melt-mixed together withoutComponent C, with or without the premixing discussed above, to produce amelt-mixture of the two components. Then, Component C separately ismixed into the blend of Components A and B. This mixture is melt-mixedto produce the reaction product. This two-step mixing can be performedin a single process, such as, for example, an extrusion process using aproper barrel length or screw configuration, along with a multiplefeeding system. In this case, Components A and B can be fed into theextruder through a main hopper to be melted and well-mixed while flowingdownstream through the extruder. Then Component C can be fed into theextruder to react with the mixture of Components A and B between thefeeding port for Component C and the die head of the extruder. The finalpolymer composition then exits from the die. If desired, any extra stepsof melt-mixing can be added to either approach of the method of thepresent invention to provide for improved mixing or completion of thereaction between Components A and C. Also, additional componentsdiscussed above can be incorporated either into a premix, or at any ofthe melt-mixing stages. Alternatively, Components A, B, and C can bemelt-mixed simultaneously to form in-situ a pseudo-crosslinked structureof Component A in the presence of Component B, either as a fully orsemi-interpenetrating network.

Illustrative polyamides for use in the compositions/golf balls disclosedinclude those obtained by: (1) polycondensation of (a) a dicarboxylicacid, such as oxalic acid, adipic acid, sebacic acid, terephthalic acid,isophthalic acid, or 1,4-cyclohexanedicarboxylic acid, with (b) adiamine, such as ethylenediamine, tetramethylenediamine,pentamethylenediamine, hexamethylenediamine, decamethylenediamine,1,4-cyclohexyldiamine or m-xylylenediamine; (2) a ring-openingpolymerization of cyclic lactam, such as ϵ-caprolactam or ω-laurolactam;(3) polycondensation of an aminocarboxylic acid, such as 6-aminocaproicacid, 9-aminononanoic acid, 11-aminoundecanoic acid or12-aminododecanoic acid; (4) copolymerization of a cyclic lactam with adicarboxylic acid and a diamine; or any combination of (1)-(4). Incertain examples, the dicarboxylic acid may be an aromatic dicarboxylicacid or a cycloaliphatic dicarboxylic acid. In certain examples, thediamine may be an aromatic diamine or a cycloaliphatic diamine Specificexamples of suitable polyamides include polyamide 6; polyamide 11;polyamide 12; polyamide 4,6; polyamide 6,6; polyamide 6,9; polyamide6,10; polyamide 6,12; polyamide MXD6; PA12,CX; PA12, IT; PPA; PA6, IT;and PA6/PPE.

The polyamide may be any homopolyamide or copolyamide. One example of agroup of suitable polyamides is thermoplastic polyamide elastomers.Thermoplastic polyamide elastomers typically are copolymers of apolyamide and polyester or polyether. For example, the thermoplasticpolyamide elastomer can contain a polyamide (Nylon 6, Nylon 66, Nylon11, Nylon 12 and the like) as a hard segment and a polyether orpolyester as a soft segment. In one specific example, the thermoplasticpolyamides are amorphous copolyamides based on polyamide (PA 12).

One class of copolyamide elastomers are polyether amide elastomers.Illustrative examples of polyether amide elastomers are those thatresult from the copolycondensation of polyamide blocks having reactivechain ends with polyether blocks having reactive chain ends, including:

(1) polyamide blocks of diamine chain ends with polyoxyalkylenesequences of dicarboxylic chains;

(2) polyamide blocks of dicarboxylic chain ends with polyoxyalkylenesequences of diamine chain ends obtained by cyanoethylation andhydrogenation of polyoxyalkylene alpha-omega dihydroxylated aliphaticsequences known as polyether diols; and

(3) polyamide blocks of dicarboxylic chain ends with polyether diols,the products obtained, in this particular case, beingpolyetheresteramides.

More specifically, the polyamide elastomer can be prepared bypolycondensation of the components (i) a diamine and a dicarboxylate,lactames or an amino dicarboxylic acid (PA component), (ii) apolyoxyalkylene glycol such as polyoxyethylene glycol, polyoxy propyleneglycol (PG component) and (iii) a dicarboxylic acid.

The polyamide blocks of dicarboxylic chain ends come, for example, fromthe condensation of alpha-omega aminocarboxylic acids of lactam or ofcarboxylic diacids and diamines in the presence of a carboxylic diacidwhich limits the chain length. The molecular weight of the polyamidesequences is preferably between about 300 and 15,000, and morepreferably between about 600 and 5,000. The molecular weight of thepolyether sequences is preferably between about 100 and 6,000, and morepreferably between about 200 and 3,000.

The amide block polyethers may also comprise randomly distributed units.These polymers may be prepared by the simultaneous reaction of polyetherand precursor of polyamide blocks. For example, the polyether diol mayreact with a lactam (or alpha-omega amino acid) and a diacid whichlimits the chain in the presence of water. A polymer is obtained thathas primarily polyether blocks and/or polyamide blocks of very variablelength, but also the various reactive groups that have reacted in arandom manner and which are distributed statistically along the polymerchain.

Suitable amide block polyethers include those as disclosed in U.S. Pat.Nos. 4,331,786; 4,115,475; 4,195,015; 4,839,441; 4,864,014; 4,230,848and 4,332,920.

The polyether may be, for example, a polyethylene glycol (PEG), apolypropylene glycol (PPG), or a polytetramethylene glycol (PTMG), alsodesignated as polytetrahydrofurane (PTHF). The polyether blocks may bealong the polymer chain in the form of diols or diamines However, forreasons of simplification, they are designated PEG blocks, or PPGblocks, or also PTMG blocks.

The polyether block comprises different units such as units which derivefrom ethylene glycol, propylene glycol, or tetramethylene glycol.

The amide block polyether comprises at least one type of polyamide blockand one type of polyether block. Mixing of two or more polymers withpolyamide blocks and polyether blocks may also be used. The amide blockpolyether also can comprise any amide structure made from the methoddescribed on the above.

Preferably, the amide block polyether is such that it represents themajor component in weight, i.e., that the amount of polyamide which isunder the block configuration and that which is eventually distributedstatistically in the chain represents 50 weight percent or more of theamide block polyether. Advantageously, the amount of polyamide and theamount of polyether is in a ratio (polyamide/polyether) of 1/1 to 3/1.

One type of polyetherester elastomer is the family of Pebax, which areavailable from Elf-Atochem Company. Preferably, the choice can be madefrom among Pebax 2533, 3533, 4033, 1205, 7033 and 7233. Blends orcombinations of Pebax 2533, 3533, 4033, 1205, 7033 and 7233 can also beprepared, as well. Pebax 2533 has a hardness of about 25 shore D(according to ASTM D-2240), a Flexural Modulus of 2.1 kpsi (according toASTM D-790), and a Bayshore resilience of about 62% (according to ASTMD-2632). Pebax 3533 has a hardness of about 35 shore D (according toASTM D-2240), a Flexural Modulus of 2.8 kpsi (according to ASTM D-790),and a Bayshore resilience of about 59% (according to ASTM D-2632). Pebax7033 has a hardness of about 69 shore D (according to ASTM D-2240) and aFlexural Modulus of 67 kpsi (according to ASTM D-790). Pebax 7333 has ahardness of about 72 shore D (according to ASTM D-2240) and a FlexuralModulus of 107 kpsi (according to ASTM D-790).

Some examples of suitable polyamides for use include those commerciallyavailable under the tradenames PEBAX, CRISTAMID and RILSAN marketed byAtofina Chemicals of Philadelphia, Pa., GRIVORY and GRILAMID marketed byEMS Chemie of Sumter, South Carolina, TROGAMID and VESTAMID availablefrom Degussa, and ZYTEL marketed by E.I. DuPont de Nemours & Co., ofWilmington, Del.

The layer or core compositions can also incorporate one or more fillers.Such fillers are typically in a finely divided form, for example, in asize generally less than about 20 mesh, preferably less than about 100mesh U.S. standard size, except for fibers and flock, which aregenerally elongated. Flock and fiber sizes should be small enough tofacilitate processing. Filler particle size will depend upon desiredeffect, cost, ease of addition, and dusting considerations. Theappropriate amounts of filler required will vary depending on theapplication but typically can be readily determined without undueexperimentation.

The filler preferably is selected from the group consisting ofprecipitated hydrated silica, limestone, clay, talc, asbestos, barytes,glass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate,zinc sulfide, lithopone, silicates, silicon carbide, diatomaceous earth,carbonates such as calcium or magnesium or barium carbonate, sulfatessuch as calcium or magnesium or barium sulfate, metals, includingtungsten steel copper, cobalt or iron, metal alloys, tungsten carbide,metal oxides, metal stearates, and other particulate carbonaceousmaterials, and any and all combinations thereof. Preferred examples offillers include metal oxides, such as zinc oxide and magnesium oxide. Inanother preferred embodiment the filler comprises a continuous ornon-continuous fiber. In another preferred embodiment the fillercomprises one or more so called nanofillers, as described in U.S. Pat.No. 6,794,447 and U.S. Patent Publication No. 2004-0092336A1 publishedMay 13, 2004 and U.S. Patent Publication No. 2005-0059756A1 publishedMar. 17, 2005, the entire contents of each of which are hereinincorporated by reference.

Inorganic nanofiller material generally is made of clay, such ashydrotalcite, phyllosilicate, saponite, hectorite, beidellite,stevensite, vermiculite, halloysite, mica, montmorillonite,micafluoride, or octosilicate. To facilitate incorporation of thenanofiller material into a polymer material, either in preparingnanocomposite materials or in preparing polymer-based golf ballcompositions, the clay particles generally are coated or treated by asuitable compatibilizing agent. The compatibilizing agent allows forsuperior linkage between the inorganic and organic material, and it alsocan account for the hydrophilic nature of the inorganic nanofillermaterial and the possibly hydrophobic nature of the polymer.Compatibilizing agents may exhibit a variety of different structuresdepending upon the nature of both the inorganic nanofiller material andthe target matrix polymer. Non-limiting examples include hydroxy-,thiol-, amino-, epoxy-, carboxylic acid-, ester-, amide-, andsiloxy-group containing compounds, oligomers or polymers. The nanofillermaterials can be incorporated into the polymer either by dispersion intothe particular monomer or oligomer prior to polymerization, or by meltcompounding of the particles into the matrix polymer. Examples ofcommercial nanofillers are various Cloisite grades including 10A, 15A,20A, 25A, 30B, and NA+ of Southern Clay Products (Gonzales, Tex.) andthe Nanomer grades including 1.24TL and C.30EVA of Nanocor, Inc.(Arlington Heights, Ill.).

As mentioned above, the nanofiller particles have an aggregate structurewith the aggregates particle sizes in the micron range and above.However, these aggregates have a stacked plate structure with theindividual platelets being roughly 1 nanometer (nm) thick and 100 to1000 nm across. As a result, nanofillers have extremely high surfacearea, resulting in high reinforcement efficiency to the material at lowloading levels of the particles. The sub-micron-sized particles enhancethe stiffness of the material, without increasing its weight or opacityand without reducing the material's low-temperature toughness.

Nanofillers when added into a matrix polymer, can be mixed in threeways. In one type of mixing there is dispersion of the aggregatestructures within the matrix polymer, but on mixing no interaction ofthe matrix polymer with the aggregate platelet structure occurs, andthus the stacked platelet structure is essentially maintained. As usedherein, this type of mixing is defined as “undispersed”.

However, if the nanofiller material is selected correctly, the matrixpolymer chains can penetrate into the aggregates and separate theplatelets, and thus when viewed by transmission electron microscopy orx-ray diffraction, the aggregates of platelets are expanded. At thispoint the nanofiller is said to be substantially evenly dispersed withinand reacted into the structure of the matrix polymer. This level ofexpansion can occur to differing degrees. If small amounts of the matrixpolymer are layered between the individual platelets then, as usedherein, this type of mixing is known as “intercalation”.

In some cases, further penetration of the matrix polymer chains into theaggregate structure separates the platelets, and leads to a completebreaking up of the platelet's stacked structure in the aggregate andthus when viewed by transmission electron microscopy (TEM), theindividual platelets are thoroughly mixed throughout the matrix polymer.As used herein, this type of mixing is known as “exfoliated”. Anexfoliated nanofiller has the platelets fully dispersed throughout thepolymer matrix; the platelets may be dispersed unevenly but preferablyare dispersed evenly.

While not wishing to be limited to any theory, one possible explanationof the differing degrees of dispersion of such nanofillers within thematrix polymer structure is the effect of the compatibilizer surfacecoating on the interaction between the nanofiller platelet structure andthe matrix polymer. By careful selection of the nanofiller it ispossible to vary the penetration of the matrix polymer into the plateletstructure of the nanofiller on mixing. Thus, the degree of interactionand intrusion of the polymer matrix into the nanofiller controls theseparation and dispersion of the individual platelets of the nanofillerwithin the polymer matrix. This interaction of the polymer matrix andthe platelet structure of the nanofiller is defined herein as thenanofiller “reacting into the structure of the polymer” and thesubsequent dispersion of the platelets within the polymer matrix isdefined herein as the nanofiller “being substantially evenly dispersed”within the structure of the polymer matrix.

If no compatibilizer is present on the surface of a filler such as aclay, or if the coating of the clay is attempted after its addition tothe polymer matrix, then the penetration of the matrix polymer into thenanofiller is much less efficient, very little separation and nodispersion of the individual clay platelets occurs within the matrixpolymer.

As used herein, a “nanocomposite” is defined as a polymer matrix havingnanofiller intercalated or exfoliated within the matrix. Physicalproperties of the polymer will change with the addition of nanofillerand the physical properties of the polymer are expected to improve evenmore as the nanofiller is dispersed into the polymer matrix to form ananocomposite.

Materials incorporating nanofiller materials can provide these propertyimprovements at much lower densities than those incorporatingconventional fillers. For example, a nylon-6 nanocomposite materialmanufactured by RTP Corporation of Wichita, Kansas uses a 3% to 5% clayloading and has a tensile strength of 11,800 psi and a specific gravityof 1.14, while a conventional 30% mineral-filled material has a tensilestrength of 8,000 psi and a specific gravity of 1.36. Because use ofnanocomposite materials with lower loadings of inorganic materials thanconventional fillers provides the same properties, this use allowsproducts to be lighter than those with conventional fillers, whilemaintaining those same properties.

Nanocomposite materials are materials incorporating from about 0.1% toabout 20%, preferably from about 0.1% to about 15%, and most preferablyfrom about 0.1% to about 10% of nanofiller reacted into andsubstantially dispersed through intercalation or exfoliation into thestructure of an organic material, such as a polymer, to providestrength, temperature resistance, and other property improvements to theresulting composite. Descriptions of particular nanocomposite materialsand their manufacture can be found in U.S. Pat. No. 5,962,553 toEllsworth, U.S. Pat. No. 5,385,776 to Maxfield et al., and U.S. Pat. No.4,894,411 to Okada et al. Examples of nanocomposite materials currentlymarketed include M1030D, manufactured by Unitika Limited, of Osaka,Japan, and 1015C2, manufactured by UBE America of New York, N.Y.

When nanocomposites are blended with other polymer systems, thenanocomposite may be considered a type of nanofiller concentrate.However, a nanofiller concentrate may be more generally a polymer intowhich nanofiller is mixed; a nanofiller concentrate does not requirethat the nanofiller has reacted and/or dispersed evenly into the carrierpolymer.

Preferably the nanofiller material is added to the polymeric compositionin an amount of from about 0.1% to about 20%, preferably from about 0.1%to about 15%, and most preferably from about 0.1% to about 10% by weightof nanofiller reacted into and substantially dispersed throughintercalation or exfoliation into the structure of the polymericcomposition.

If desired, the various polymer compositions used to prepare the golfballs can additionally contain other additives such as plasticizers,pigments, antioxidants, U.V. absorbers, optical brighteners, or anyother additives generally employed in plastics formulation or thepreparation of golf balls.

Another particularly well-suited additive for use in the presentlydisclosed compositions includes compounds having the general formula:

(R₂N)_(m)—R′—(X(O)_(n)OR_(y))_(m),

where R is hydrogen, or a C₁-C₂₀ aliphatic, cycloaliphatic or aromaticsystems; R′ is a bridging group comprising one or more C₁-C₂₀ straightchain or branched aliphatic or alicyclic groups, or substituted straightchain or branched aliphatic or alicyclic groups, or aromatic group, oran oligomer of up to 12 repeating units including, but not limited to,polypeptides derived from an amino acid sequence of up to 12 aminoacids; and X is C or S or P with the proviso that when X=C, n=1 and y=1and when X=S, n=2 and y=1, and when X=P, n=2 and y=2. Also, m=1-3. Thesematerials are more fully described in copending U.S. Provisional PatentApplication No. 60/588,603, filed on Jul. 16, 2004, the entire contentsof which are herein incorporated by reference. These materials includecaprolactam, oenantholactam, decanolactam, undecanolactam,dodecanolactam, caproic 6-amino acid, 11-aminoundecanoicacid,12-aminododecanoic acid, diamine hexamethylene salts of adipic acid,azeleic acid, sebacic acid and 1,12-dodecanoic acid and the diaminenonamethylene salt of adipic acid., 2-aminocinnamic acid, L-asparticacid, 5-aminosalicylic acid, aminobutyric acid; aminocaproic acid;aminocapyryic acid; 1-(aminocarbonyl)-1-cyclopropanecarboxylic acid;aminocephalosporanic acid; aminobenzoic acid; aminochlorobenzoic acid;2-(3-amino-4-chlorobenzoyl)benzoic acid; aminonaphtoic acid;aminonicotinic acid; aminonorbornanecarboxylic acid; aminoorotic acid;aminopenicillanic acid; aminopentenoic acid; (aminophenyl)butyric acid;aminophenyl propionic acid; aminophthalic acid; aminofolic acid;aminopyrazine carboxylic acid; aminopyrazole carboxylic acid;aminosalicylic acid; aminoterephthalic acid; aminovaleric acid; ammoniumhydrogencitrate; anthranillic acid; aminobenzophenone carboxylic acid;aminosuccinamic acid, epsilon-caprolactam; omega-caprolactam,(carbamoylphenoxy)acetic acid, sodium salt; carbobenzyloxy asparticacid; carbobenzyl glutamine; carbobenzyloxyglycine; 2-aminoethylhydrogensulfate; aminonaphthalenesulfonic acid; aminotoluene sulfonicacid; 4,4′-methylene-bis-(cyclohexylamine)carbamate and ammoniumcarbamate.

Most preferably the material is selected from the group consisting of4,4′-methylene-bis-(cyclohexylamine)carbamate (commercially availablefrom R.T. Vanderbilt Co., Norwalk, Conn. under the tradename Diak® 4),11-aminoundecanoicacid, 12-aminododecanoic acid, epsilon-caprolactam;omega-caprolactam, and any and all combinations thereof.

In an especially preferred embodiment a nanofiller additive component inthe golf ball is surface modified with a compatibilizing agentcomprising the earlier described compounds having the general formula:

(R₂N)_(m)—R′—(X(O)_(n)OR_(y))_(m),

A most preferred embodiment would be a filler comprising a nanofillerclay material surface modified with an amino acid including12-aminododecanoic acid. Such fillers are available from Nanonocor Co.under the tradename Nanomer 1.24TL.

Prior to its use in golf balls, the core and/or layer compositions maybe further formulated with one or more of the following blendcomponents:

B. Cross-Linking Agents

Any crosslinking or curing system typically used for crosslinking may beused to crosslink the polymer(s), if desired. Satisfactory crosslinkingsystems are based on sulfur-, peroxide-, azide-, maleimide- orresin-vulcanization agents, which may be used in conjunction with avulcanization accelerator. Examples of satisfactory crosslinking systemcomponents are zinc oxide, sulfur, organic peroxide, azo compounds,magnesium oxide, benzothiazole sulfenamide accelerator, benzothiazyldisulfide, phenolic curing resin, m-phenylene bis-maleimide, thiuramdisulfide and dipentamethylene-thiuram hexasulfide.

More preferable cross-linking agents include peroxides, sulfurcompounds, as well as mixtures of these. Non-limiting examples ofsuitable cross-linking agents include primary, secondary, or tertiaryaliphatic or aromatic organic peroxides. Peroxides containing more thanone peroxy group can be used, such as2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-di-(2-tert-butylperoxyisopropyl)benzene. Both symmetrical and asymmetrical peroxides canbe used, for example, tert-butyl perbenzoate and tert-butyl cumylperoxide. Peroxides incorporating carboxyl groups also are suitable. Thedecomposition of peroxides used as cross-linking agents in the disclosedcompositions can be brought about by applying thermal energy, shear,irradiation (e.g., ultra violet-active agents or electron beam-activeagents), reaction with other chemicals, or any combination of these.Both homolytically and heterolytically decomposed peroxide can be used.Non-limiting examples of suitable peroxides include: diacetyl peroxide;di-tert-butyl peroxide; dibenzoyl peroxide; dicumyl peroxide;2,5-dimethyl-2,5-di(benzoylperoxy)hexane;1,4-bis-(t-butylperoxyisopropyl)benzene; t-butylperoxybenzoate;2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3, such as Trigonox 145-45B,marketed by Akrochem Corp. of Akron, Ohio; 1,1-bis(t-butylperoxy)-3,3,5tri-methylcyclohexane, such as Varox 231-XL, marketed by R.T. VanderbiltCo., Inc. of Norwalk, Conn.; and di-(2,4-dichlorobenzoyl)peroxide.

The cross-linking agents can be blended in total amounts of about 0.01part to about 5 parts, more preferably about 0.05 part to about 4 parts,and most preferably about 0.1 part to about 2 parts, by weight of thecross-linking agents per 100 parts by weight of the polymer-containingcomposition.

In a further embodiment, the cross-linking agents can be blended intotal amounts of about 0.05 part to about 5 parts, more preferably about0.2 part to about 3 parts, and most preferably about 0.2 part to about 2parts, by weight of the cross-linking agents per 100 parts by weight ofthe polymer-containing composition.

Each peroxide cross-linking agent has a characteristic decompositiontemperature at which 50% of the cross-linking agent has decomposed whensubjected to that temperature for a specified time period (t_(½)). Forexample, 1,1-bis-(t-butylperoxy)-3,3,5-tri-methylcyclohexane att_(½)=0.1 hour has a decomposition temperature of 138° C. and2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3 at t_(½)=0.1 hour has adecomposition temperature of 182° C. Two or more cross-linking agentshaving different characteristic decomposition temperatures at the samet_(½) may be blended in the composition. For example, where at least onecross-linking agent has a first characteristic decomposition temperatureless than 150° C., and at least one cross-linking agent has a secondcharacteristic decomposition temperature greater than 150° C., thecomposition weight ratio of the at least one cross-linking agent havingthe first characteristic decomposition temperature to the at least onecross-linking agent having the second characteristic decompositiontemperature can range from 5:95 to 95:5, or more preferably from 10:90to 50:50.

Besides the use of chemical cross-linking agents, exposure of thepolymer-containing composition to radiation also can serve as across-linking agent. Radiation can be applied to the polymer-containingcomposition by any known method, including using microwave or gammaradiation, or an electron beam device. Additives may also be used toimprove radiation-induced crosslinking of the polymer-containingcomposition.

C. Co-Cross-Linking Agent

The polymer containing-composition may also be blended with aco-cross-linking agent, which may be a metal salt of an unsaturatedcarboxylic acid. Examples of these include zinc and magnesium salts ofunsaturated fatty acids having 3 to 8 carbon atoms, such as acrylicacid, methacrylic acid, maleic acid, and fumaric acid, palmitic acidwith the zinc salts of acrylic and methacrylic acid being mostpreferred. The unsaturated carboxylic acid metal salt can be blended inthe polymer-containing composition either as a preformed metal salt, orby introducing an α,β-unsaturated carboxylic acid and a metal oxide orhydroxide into the polymer-containing composition, and allowing them toreact to form the metal salt. The unsaturated carboxylic acid metal saltcan be blended in any desired amount, but preferably in amounts of about1 part to about 100 parts by weight of the unsaturated carboxylic acidper 100 parts by weight of the polymer-containing composition.

D. Peptizer

The polymer-containing composition may also incorporate one or more ofthe so-called “peptizers”.

The peptizer preferably comprises an organic sulfur compound and/or itsmetal or non-metal salt. Examples of such organic sulfur compoundsinclude thiophenols, such as pentachlorothiophenol,4-butyl-o-thiocresol, 4 t-butyl-p-thiocresol, and 2-benzamidothiophenol;thiocarboxylic acids, such as thiobenzoic acid; 4,4′ dithiodimorpholine; and, sulfides, such as dixylyl disulfide, dibenzoyldisulfide; dibenzothiazyl disulfide; di(pentachlorophenyl) disulfide;dibenzamido diphenyldisulfide (DBDD), and alkylated phenol sulfides,such as VULTAC marketed by Atofina Chemicals, Inc. of Philadelphia, Pa.Preferred organic sulfur compounds include pentachlorothiophenol, anddibenzamido diphenyldisulfide.

Examples of the metal salt of an organic sulfur compound include sodium,potassium, lithium, magnesium calcium, barium, cesium and zinc salts ofthe above-mentioned thiophenols and thiocarboxylic acids, with the zincsalt of pentachlorothiophenol being most preferred.

Examples of the non-metal salt of an organic sulfur compound includeammonium salts of the above-mentioned thiophenols and thiocarboxylicacids wherein the ammonium cation has the general formula [NR¹R²R³R⁴]⁺where R¹, R², R³ and Ware selected from the group consisting ofhydrogen, a C₁-C₂₀ aliphatic, cycloaliphatic or aromatic moiety, and anyand all combinations thereof, with the most preferred being the NH₄⁺-salt of pentachlorothiophenol.

Additional peptizers include aromatic or conjugated peptizers comprisingone or more heteroatoms, such as nitrogen, oxygen and/or sulfur. Moretypically, such peptizers are heteroaryl or heterocyclic compoundshaving at least one heteroatom, and potentially plural heteroatoms,where the plural heteroatoms may be the same or different. Suchpeptizers include peptizers such as an indole peptizer, a quinolinepeptizer, an isoquinoline peptizer, a pyridine peptizer, purinepeptizer, a pyrimidine peptizer, a diazine peptizer, a pyrazinepeptizer, a triazine peptizer, a carbazole peptizer, or combinations ofsuch peptizers.

Suitable peptizers also may include one or more additional functionalgroups, such as halogens, particularly chlorine; a sulfur-containingmoiety exemplified by thiols, where the functional group is sulfhydrl(—SH), thioethers, where the functional group is —SR, disulfides,(R₁S—SR₂), etc.; and combinations of functional groups. Such peptizersare more fully disclosed in copending U.S. application Ser. No.60/752,475 filed on Dec. 20, 2005 in the name of Hyun Kim et al, theentire contents of which are herein incorporated by reference. A mostpreferred example is a a pyridine peptizer that also includes a chlorinefunctional group and a thiol functional group such as2,3,5,6-tetrachloro-4-pyridinethiol (TCPT).

The peptizer, if employed in the golf balls, is present in an amount offrom about 0.01 to about 10, preferably of from about 0.05 to about 7,more preferably of from about 0.1 to about 5 parts by weight per 100parts by weight of the polymer-containing composition.

E. Accelerators

The polymer-containing composition can also comprise one or moreaccelerators of one or more classes. Accelerators are added to anunsaturated polymer to increase the vulcanization rate and/or decreasethe vulcanization temperature. Accelerators can be of any class knownfor rubber processing including mercapto-, sulfenamide-, thiuram,dithiocarbamate, dithiocarbamyl-sulfenamide, xanthate, guanidine, amine,thiourea, and dithiophosphate accelerators. Specific commercialaccelerators include 2-mercaptobenzothiazole and its metal or non-metalsalts, such as Vulkacit Mercapto C, Mercapto M G C, Mercapto ZM-5, andZM marketed by Bayer AG of Leverkusen, Germany, Nocceler M, Nocceler MZ, and Nocceler M-60 marketed by Ouchisinko Chemical Industrial Company,Ltd. of Tokyo, Japan, and MBT and ZMBT marketed by Akrochem Corporationof Akron, Ohio. A more complete list of commercially availableaccelerators is given in The Vanderbilt Rubber Handbook: 13^(th) Edition(1990, R.T. Vanderbilt Co.), pp. 296-330, in Encyclopedia of PolymerScience and Technology, Vol. 12 (1970, John Wiley & Sons), pp. 258-259,and in Rubber Technology Handbook (1980, Hanser/Gardner Publications),pp. 234-236. Preferred accelerators include 2-mercaptobenzothiazole(MBT) and its salts.

The polymer-containing composition can further incorporate from about0.01 part to about 10 parts by weight of the accelerator per 100 partsby weight of the polymer-containing composition. More preferably, theball composition can further incorporate from about 0.02 part to about 5parts, and most preferably from about 0.03 part to about 1.5 parts, byweight of the accelerator per 100 parts by weight of the polymer.

Golf Ball Composition and Construction

Referring to the drawing in FIG. 1, there is illustrated a golf ball 1,which comprises a solid center or core 2, which may be formed as a solidbody and in the shape of the sphere.

In certain embodiments, the core of the balls may have a diameter offrom 1.00 to 1.55, preferably from 1.20 to 1.50, and more preferablyfrom 1.30 to 1.40, inches.

The core of the balls also may have a PGA compression of less than 80,preferably less than 70, more preferably less than 60, most preferablyless than 50, and particularly less than 40. The PGA compression of thecores may range from 20 to 80, and preferably from 30 to 40.

In certain embodiments, the flexural modulus of the core material may beless than 20 kpsi, particularly less than about 15 kpsi, preferably lessthan 10 kpsi, and most preferably less than 8 kpsi.

The various core layer materials (including the center) may each exhibita different material hardness. The difference between the centerhardness and that of the next adjacent layer, as well as the differencein hardness between the various core layers may be greater than 2,preferably greater than 5, most preferably greater than 10 units ofShore D. In one preferred embodiment, the hardness of the center andeach sequential layer increases progressively outwards from the centerto outer core layer. In another preferred embodiment, the hardness ofthe center and each sequential layer decreases progressively inward fromthe outer core layer to the center. The core may be a solid core or awound core.

Any combination of the above-described property ranges for the core maybe employed, but illustrative specific embodiments of the core include adiameter of 1.00 to 1.55 inches, a PGA compression of less than 50, anda flexural modulus less than 15 kpsi; a diameter of 1.00 to 1.55 inches,a PGA compression of less than 50, and a flexural modulus less than 8kpsi; and a diameter of 1.00 to 1.55 inches, a PGA compression of lessthan 40, and a flexural modulus less than 8 kpsi.

The core may be made from any of the polymers described above. Incertain embodiments, the core is made from polybutadiene. In particularexamples, the polybutadiene is the “major ingredient” of the coremeaning that the polybutadiene constitutes at least 50, moreparticularly 60, most particularly 80, wt %, of all the ingredients inthe core. In further embodiments, polybutadiene is the only polymerpresent in the core.

Mantle Layers

Again referring to the drawing in FIG. 1, there is illustrated a golfball 1, which comprises a solid center or core 2, which may be formed asa solid body and in the shape of the sphere, an inner mantle layer 3disposed adjacent to the spherical core, an intermediate mantle layer 4,and an outer mantle layer 5.

Each of the mantle layers of the golf balls may have a thickness of lessthan 0.080 inch, more particularly less than 0.065 inch, and mostparticularly less than 0.055 inch.

In certain embodiments the inner mantle may have a material Shore Dhardness of 15 to 65, particularly 25 to 60, and more particularly 30 to58. The inner mantle may have a flexural modulus of 2 to 35,particularly 10 to 30, and more particularly 15 to 35, kpsi. Theintermediate mantle may have a flexural modulus of 10 to 50,particularly 25 to 50, and most particularly 25 to 40, kpsi, and amaterial Shore D hardness of 40 to 70, more particularly from 45 to 65,and most particularly from 50 to 60. The outer mantle may have amaterial Shore D hardness of 55 to 75, particularly 58 to 70, and moreparticularly 60 to 68. The outer mantle material may have a flexuralmodulus of 30 to 80, particularly 40 to 80, and most particularly 50 to75, kpsi.

The mantle layer may be made from any suitable material, particularlythose materials described herein. In certain examples, the mantle layersmay include a unimodal ionomer; a bimodal ionomer; a modified unimodalionomer; a modified bimodal ionomer; a thermoset polyurethane; apolyester elastomer; a copolymer comprising at least one firstco-monomer selected from butadiene, isoprene, ethylene or butylene andat least one second co-monomer selected from a (meth)acrylate or a vinylarylene; a polyalkenamer; or any and all combinations or mixturesthereof. The above-listed mantle layer material(s) may be the “majoringredient” of the mantle layer meaning that the material(s) constitutesat least 50, more particularly 60, most particularly 80, wt %, of allthe ingredients in the mantle layer. In further embodiments, theabove-listed mantle layer material(s) is the only polymer(s) present inthe mantle layer(s).

Cover Layer(s)

The cover layer of the balls may have a thickness of about 0.01 to about0.10, preferably from about 0.02 to about 0.08, more preferably fromabout 0.03 to about 0.06 inch.

The cover layer of the balls may have a hardness Shore D from about 40to about 70, preferably from about 45 to about 70 or about 50 to about70, more preferably from 47 to about 68 or about 45 to about 70, andmost preferably from about 50 to about 65.

The cover layer may be made from any suitable material, particularlythose disclosed herein. In preferred embodiments, illustrative examplesinclude a thermoplastic elastomer, a thermoset polyurethane, athermoplastic polyurethane, a unimodal ionomer, a bimodal ionomer, amodified unimodal ionomer, a modified bimodal ionomer; or any and allcombinations or mixtures thereof. The above-listed cover layermaterial(s) may be the “major ingredient” of the cover layer meaningthat the material(s) constitutes at least 50, more particularly 60, mostparticularly 80, wt %, of all the ingredients in the cover layer. Infurther embodiments, the above-listed cover layer material(s) is theonly polymer(s) present in the cover layer(s).

A coating layer may be disposed on, or adjacent to, the outer coverlayer. For example, the coating layer may be a thermoplastic resin basedpaint and/or a thermosetting resin based paint. Examples of such paintsinclude vinyl acetate resin paints, vinyl acetate copolymer resinpaints, EVA (ethylene-vinyl acetate copolymer resin) paints, acrylicester (co)polymer resin paints, epoxy resin paints, thermosettingurethane resin paints, thermoplastic urethane resin paints,thermosetting acrylic resin paints, and unsaturated polyester resinpaints. The coating layer may be transparent, semi-transparent ortranslucent.

The coefficient of restitution (“COR”) of the golf balls may be greaterthan about 0.700, preferably greater than about 0.740, more preferablygreater than 0.760, yet more preferably greater than 0.780, mostpreferably greater than 0.795, and especially greater than 0.800 at 125ft/sec inbound velocity. In another embodiment, the COR of the golfballs may be greater than about 0.700, preferably greater than about0.740, more preferably greater than 0.760, yet more preferably greaterthan 0.780, most preferably greater than 0.790, and especially greaterthan 0.800 at 143 ft/sec inbound velocity.

Method of Making the Golf Balls

The polymer(s), crosslinking agent(s), filler(s) and the like can bemixed together with or without melting them. Dry blending equipment,such as a tumble mixer, V-blender, ribbon blender, or two-roll mill, canbe used to mix the compositions. The golf ball compositions can also bemixed using a mill, internal mixer such as a Banbury or Farrelcontinuous mixer, extruder or combinations of these, with or withoutapplication of thermal energy to produce melting. The various componentscan be mixed together with the cross-linking agents, or each additivecan be added in an appropriate sequence to the milled unsaturatedpolymer. In another method of manufacture the cross-linking agents andother components can be added to the unsaturated polymer as part of aconcentrate using dry blending, roll milling, or melt mixing.

The resulting mixture can be subjected to, for example, a compression orinjection molding process, to obtain solid spheres for the core. Thepolymer mixture is subjected to a molding cycle in which heat andpressure are applied while the mixture is confined within a mold. Thecavity shape depends on the portion of the golf ball being formed. Thecompression and heat liberates free radicals by decomposing one or moreperoxides, which initiate cross-linking The temperature and duration ofthe molding cycle are selected based upon the type of peroxide selected.The molding cycle may have a single step of molding the mixture at asingle temperature for fixed time duration.

After core formation, the golf ball cover and any mantle layers aretypically positioned over the core using one of three methods: casting,injection molding, or compression molding. Injection molding generallyinvolves using a mold having one or more sets of two hemispherical moldsections that mate to form a spherical cavity during the moldingprocess. The pairs of mold sections are configured to define a sphericalcavity in their interior when mated. When used to mold an outer coverlayer for a golf ball, the mold sections can be configured so that theinner surfaces that mate to form the spherical cavity includeprotrusions configured to form dimples on the outer surface of themolded cover layer. When used to mold a layer onto an existingstructure, such as a ball core, the mold includes a number of supportpins disposed throughout the mold sections. The support pins areconfigured to be retractable, moving into and out of the cavityperpendicular to the spherical cavity surface. The support pins maintainthe position of the core while the molten material flows through thegates into the cavity between the core and the mold sections. The molditself may be a cold mold or a heated mold

Compression molding of a ball cover or mantle layer typically requiresthe initial step of making half shells by injection molding the layermaterial into an injection mold. The half shells then are positioned ina compression mold around a ball core, whereupon heat and pressure areused to mold the half shells into a complete layer over the core, withor without a chemical reaction such as crosslinking Compression moldingalso can be used as a curing step after injection molding. In such aprocess, an outer layer of thermally curable material is injectionmolded around a core in a cold mold. After the material solidifies, theball is removed and placed into a mold, in which heat and pressure areapplied to the ball to induce curing in the outer layer.

In certain specific embodiments, the core comprises polybutadiene;

-   -   the inner mantle layer and the intermediate mantle layer each        individually comprise a unimodal ionomer; a bimodal ionomer; a        modified unimodal ionomer; a modified bimodal ionomer; a        thermoset polyurethane; a polyester elastomer; a copolymer        comprising at least one first co-monomer selected from        butadiene, isoprene, ethylene, propylene or butylene and at        least one second co-monomer selected from a (meth)acrylate or a        vinyl arylene; a polyalkenamer; or any and all combinations or        mixtures thereof;    -   the outer mantle layer comprises a copolymer of ethylene and        (meth)acrylic acid partially neutralized with a metal selected        from the group consisting of lithium, sodium, potassium,        magnesium, calcium, barium, lead, tin, zinc, aluminum or a        combination thereof; or a blend of a polyamide and at least one        maleic anhydride grafted polyolefin; and    -   the outer cover layer comprises a thermoset polyurethane; a        thermoset polyurea; a polymer blend composition formed from a        copolymer of ethylene and carboxylic acid as Component A, a        hydroxyl-modified block copolymer of styrene and isoprene as        Component B, and a metal cation as Component C; or a polymer        blend composition formed from a copolymer of ethylene and        carboxylic acid as Component A, a        styrene-(ethylene-butylene)-styrene block copolymer as Component        B, and a metal cation as Component C.

In particular examples, the materials listed immediately above are theonly polymers present in the core, inner mantle layer, intermediatemantle layer, outer mantle layer, and cover layer, respectively.

EXAMPLES Example A

One example of a ball includes a core having a PGA compression of 35 anda flexural modulus of 5 kpsi, an inner mantle having a PGA compressionof 55 and a flexural modulus of 31, an intermediate mantle having a PGAcompression of 72 and a flexural modulus of 45 kpsi, an outer mantlehaving a PGA compression of 96 and a flexural modulus of 59.5 kpsi, andan outer cover layer having a PGA compression of 96 and a flexuralmodulus of 11.3 kpsi.

Shore D hardness can be measured in accordance with ASTM D2240. Hardnessof a layer can be measured on the ball, perpendicular to a land areabetween the dimples (referred to as “on-the-ball” hardness). The Shore Dhardness of a material prior to fabrication into a ball layer can alsobe measured (referred to as “material” hardness).

Core or ball diameter may be determined using standard linear calipersor a standard size gauge.

Compression may be measured by applying a spring-loaded force to thesphere to be examined, with a manual instrument (an “Atti gauge”)manufactured by the Atti Engineering Company of Union City, N.J. Thismachine, equipped with a Federal Dial Gauge, Model D81-C, employs acalibrated spring under a known load. The sphere to be tested is forceda distance of 0.2 inch (5 mm) against this spring. If the spring, inturn, compresses 0.2 inch, the compression is rated at 100; if thespring compresses 0.1 inch, the compression value is rated as 0. Thusmore compressible, softer materials will have lower Atti gauge valuesthan harder, less compressible materials. The value is taken shortlyafter applying the force and within at least 5 secs if possible.Compression measured with this instrument is also referred to as PGAcompression.

The approximate relationship that exists between Atti or PGA compressionand Riehle compression can be expressed as:

(Atti or PGA compression)=(160-Riehle Compression).

Thus, a Riehle compression of 100 would be the same as an Atticompression of 60.

The initial velocity of a golf ball after impact with a golf club isgoverned by the United States Golf Association (“USGA”). The USGArequires that a regulation golf ball can have an initial velocity of nomore than 250 feet per second ±2% or 255 feet per second. The USGAinitial velocity limit is related to the ultimate distance that a ballmay travel (280 yards±6%), and is also related to the coefficient ofrestitution (“COR”). The coefficient of restitution is the ratio of therelative velocity between two objects after direct impact to therelative velocity before impact. As a result, the COR can vary from 0 to1, with 1 being equivalent to a completely elastic collision and 0 beingequivalent to a completely inelastic collision. Since a ball's CORdirectly influences the ball's initial velocity after club collision andtravel distance, golf ball manufacturers are interested in thischaracteristic for designing and testing golf balls.

Golf ball Sound Pressure Level, S, in decibels (dB) and Frequency inhertz (Hz) may be measured by dropping the ball from a height of 113 inonto a marble (“starnet crystal pink”) stage of at least 12″ square and4.25 inches in thickness. The sound of the resulting impact is capturedby a microphone positioned at a fixed proximity of 12 inches, and at anangle of 30 degrees from horizontal, from the impact position andresolved by software transformation into an intensity in db and afrequency in Hz. Data collection is done as follows:

Microphone data is collected using a laptop PC with a sound card. AnA-weighting filter is applied to the analog signal from the microphone.This signal is then digitally sampled at 44.1 KHz by the laptop dataacquisition system for further processing and analysis. Data Analysiswas done as follows:

The Data Analysis is Split into Two Processes:

-   -   a. Time series analysis that generates the root mean square        (rms) sound pressure level (SPL) for each ball impact sound.        -   i. An rms SPL from a reference calibration signal is            generated in the same manner as the ball data.        -   ii. The overall SPL (in decibels) is calculated from the            reference signal for each ball impact sound.        -   iii. The median SPL is recorded based on 3 impact tests.    -   b. Spectral analyses for each ball impact sound        -   i. Fourier and Autoregressive spectral estimation techniques            are employed to create power spectra.        -   ii. The frequencies (in cycles/sec—Hz) from highest level            peaks representing the most active sound producing vibration            modes of each ball are identified.

Impact durability may be tested with an endurance test machine. Theendurance test machine is designed to impart repetitive deformation to agolf ball similar to a driver impact.

The test machine consists of an arm and impact plate or club face thatboth rotate to a speed that generates ball speeds of approximately155-160 mph. Ball speed is measured with two light sensors located 15.5″from impact location and are 11″ apart. The ball is stopped by a net andif a test sample is not cracked will continue to cycle through themachine for additional impacts. For golf balls, if zero failures occurthrough in excess of 100 impacts per ball than minimal field failureswill occur. For layers adjacent to the outer cover, fewer impacts arerequired since the cover typically “protects” the inner components ofthe golf ball. For the purpose of this study 75 impacts per component isconsidered sufficient.

Example B

Illustrative golf balls were made with the constructions shown in Table1.

TABLE 1 5 piece 3 pc 3 pc 4 pc 4 pc example example example-soft exampleexample-soft Core Size 1.300 1.480 1.500 1.420 1.420 Core Compression 4370 50 50 40 Flex Mod(kpsi) 4.0 6 5 5 5 Inner Mantle HG252 — — — —Diameter(in) 1.400 — — — — Thickness(in) 0.050 — — — — Compression (PGA)41 — — — Hardness(Shore D) 42 — — — Flex Mod(kpsi) 22.5 IntermediateMantle HPF 1000 — — HPF 1000 HPF 1000 — — Diameter(in) 1.500 — — 1.5201.520 Thickness(in) 0.050 — — 0.050 0.050 Compression (PGA) 52 — 60 46Hardness(Shore D) 52 — 52 52 Flex Mod(kpsi) 31 31 31 Outer Mantle 50%8150 50% 8150 50% 8150 50% 8150 50% 8150 50% 9150 50% 9150 50% 9150 50%9150 50% 9150 Diameter(in) 1.600 1.620 1.620 1.620 1.620 Thickness(in)0.050 0.070 0.050 0.050 0.050 Compression (PGA) 70 98 70 80 71Hardness(Shore D) 66 66 66 66 66 Flex Mod(kpsi) 60 60 60 60 60 SoundFrequency(Hz) 3150 3660 3300 3240 assume lower since softer SPL (dB)86.3 89.8 87.6 87.8 mantle compression Durability # failures at hit #0F-75x 0F-75x 1F-62x, 2F-75x 0F-75x 1F-55x, 56x, 58x, 61x, 73x

SEPTON HG 252 is a styrenic copolymer available from Kuraray AmericaInc. HPF 1000 is a modified ionomer polymer available from DuPont.Surlyn 8150 and Surlyn 9150 are ionomers polymers available from DuPont.

All the cores were made from a blend of polybutadiene, zinc oxide,barium sulfate, zinc diacrylate, peroxide and2,3,5,6-tetrachloro-4-pyridinethiol (TCPT). The cores were made by thestandard process that includes mixing the core material in a two rollmill, extruding the mixture, and then forming and curing the cores underheat and pressure in a compression molding cycle. The inner layers wereall made by injection molding. Only the mantle layers of the balls inTable 1 were tested; no balls with cover layers were tested. However,any type of cover layer could have been applied to the balls. In theexamples, the hardness measurements are on the ball/mantle

The results shown in Table 1 demonstrate that a ball with a presentlydisclosed 5-piece construction exhibits sufficient impact durability andachieves a “soft feel.”

Additional examples of the balls disclosed herein are described in thefollowing numbered paragraphs:

1. A golf ball comprising:

-   -   (a) a core;    -   (b) an inner mantle layer;    -   (c) an intermediate mantle layer;    -   (d) an outer mantle layer; and    -   (e) at least one cover layer;    -   wherein the core has a PGA compression of less than 70, and the        core/inner mantle layer/intermediate mantle layer combined        construct has a PGA compression of at least 40.

2. The golf ball of paragraph 1, wherein the core has a PGA compressionof less than 60.

3. The golf ball of paragraph 1, wherein the core has a PGA compressionof less than 50.

4. The golf ball of paragraph 1, wherein the core has a PGA compressionof less than 40.

5. The golf ball of any one of paragraphs 1 to 4, wherein each of themantle layers each have a thickness of less than 0.080 in.

6. The golf ball of any one of paragraphs 1 to 5, wherein the core/innermantle layer/intermediate mantle layer combined construct has a PGAcompression of at least 50.

7. The golf ball of any one of paragraphs 1 to 5, wherein the core/innermantle layer/intermediate mantle layer combined construct has a PGAcompression of at least 60.

8. The golf ball of any one of paragraphs 1 to 7, wherein the innermantle layer, the intermediate mantle layer, and the outer mantle layereach individually comprises a unimodal ionomer; a bimodal ionomer; amodified unimodal ionomer; a modified bimodal ionomer; a thermosetpolyurethane; a polyester elastomer; a copolymer comprising at least onefirst co-monomer selected from butadiene, isoprene, ethylene or butyleneand at least one second co-monomer selected from a (meth)acrylate or avinyl arylene; a polyalkenamer; or any and all combinations or mixturesthereof.

9. The golf ball of any one of paragraphs 1 to 8, wherein the outermantle layer has a material Shore D hardness of at least 65 and amaterial flexural modulus of at least 65 kpsi.

10. The golf ball of any of paragraphs 1 to 9, wherein each of (a), (b),(c) and (d) have a Shore D hardness and the Shore D hardness of each of(a), (b), (c) and (d) increases from the core to the outer mantle layer.

11. The golf ball of any one of paragraph 1 to 10, wherein the coverlayer comprises a polyurethane, a polyurea, or a combination or mixturethereof.

12. A golf ball comprising:

-   -   (a) a core material having a PGA compression of less than 70 and        a material flexural modulus of less than 20 kpsi;    -   (b) an inner mantle layer material;    -   (c) an intermediate mantle layer material;    -   (d) an outer mantle layer material; and    -   (e) at least one cover layer material;    -   wherein the material of each of (a), (b), (c) and (d) have a        material flexural modulus and the material flexural modulus of        each of (a), (b), (c) and (d) increases from the core material        to the outer mantle layer material such that each successive        layer between the core material and the outer mantle layer        material has a flexural modulus that is greater by at least 3        kpsi relative to the immediately adjacent inner layer material.

13. The golf ball of paragraph 12, wherein the core has a PGAcompression of less than 50.

14. The golf ball of paragraph 12, wherein the core has a PGAcompression of less than 40.

15. The golf ball of any one of paragraphs 12 to 14, wherein each of themantle layers each have a thickness of less than 0.080 in.

16. The golf ball of any one of paragraphs 12 to 14, wherein each of themantle layers each have a thickness of less than 0.055 in.

17. The golf ball of any one of paragraphs 12 to 16, wherein the innermantle layer has a material flexural modulus of 2 to 35 kpsi.

18. The golf ball of any one of paragraphs 12 to 17, wherein theintermediate mantle layer has a material flexural modulus of 10 to 50kpsi.

19. The golf ball of any one of paragraphs 12 to 18, wherein the outermantle layer has a material flexural modulus of 30 to 80 kpsi.

20. The golf ball of any one of paragraphs 12 to 19, wherein the corematerial has a flexural modulus of less than 10 kpsi and a PGAcompression of less than 40.

21. The golf ball of any one of paragraphs 12 to 20, wherein the innermantle layer, the intermediate mantle layer, and the outer mantle layereach individually comprises a unimodal ionomer; a bimodal ionomer; amodified unimodal ionomer; a modified bimodal ionomer; a thermosetpolyurethane; a polyester elastomer; a copolymer comprising at least onefirst co-monomer selected from butadiene, isoprene, ethylene or butyleneand at least one second co-monomer selected from a (meth)acrylate or avinyl arylene; a polyalkenamer; or any and all combinations or mixturesthereof.

22. The golf ball of any one of paragraphs 12 to 21, wherein the coverlayer comprises a polyurethane, a polyurea, or a combination or mixturethereof.

23. The golf ball of any one of paragraphs 11 to 20, wherein the outermantle layer has a material Shore D hardness of at least 65 and aflexural modulus of at least 65 kpsi.

24. A five-piece golf ball comprising:

-   -   (a) a core material having a flexural modulus of less than 15        kpsi;    -   (b) an inner mantle layer material adjacent to the core        material, wherein the inner mantle layer material has a flexural        modulus of 2-35 kpsi;    -   (c) an intermediate mantle layer material adjacent to the inner        mantle layer material, wherein the intermediate mantle layer        material has a flexural modulus of 10-50 kpsi;    -   (d) an outer mantle layer material adjacent to the intermediate        mantle layer material, wherein the outer mantle layer material        has a flexural modulus of 30-80; and    -   (e) an outer cover layer material.

25. The golf ball of paragraph 23, wherein the core material has aflexural modulus of less than 8 kpsi, the inner mantle layer materialhas a flexural modulus of 15-35 kpsi, the intermediate mantle layermaterial has a flexural modulus of 25-50 kpsi, and the outer mantlelayer has a flexural modulus of 50-75 kpsi.

26. The golf ball of paragraph 24 or 25, wherein there is an increasingmaterial Shore D hardness from the core material to the outer mantlelayer material, and an increasing flexural modulus from the corematerial to the outer mantle layer material.

27. The golf ball of any one of paragraphs 24 to 26, wherein the corematerial has a PGA compression of less than 50.

28. The golf ball of any one of paragraphs 22 to 27, wherein each of themantle layers each have a thickness of less than 0.080 in.

29. The golf ball of any one of paragraphs 22 to 27, wherein each of themantle layers each have a thickness of less than 0.055 in.

30. The golf ball of any one of paragraphs 22 to 29, wherein the innermantle layer, the intermediate mantle layer, and the outer mantle layereach individually comprises a unimodal ionomer; a bimodal ionomer; amodified unimodal ionomer; a modified bimodal ionomer; a thermosetpolyurethane; a polyester elastomer; a copolymer comprising at least onefirst co-monomer selected from butadiene, isoprene, ethylene or butyleneand at least one second co-monomer selected from a (meth)acrylate or avinyl arylene; a polyalkenamer; or any and all combinations or mixturesthereof.

31. The golf ball of any one of paragraphs 22 to 30, wherein the coverlayer comprises a polyurethane, a polyurea, or a combination or mixturethereof.

32. The golf ball of any one of paragraphs 22 to 31, wherein the outermantle layer has a material Shore D hardness of at least 65 and aflexural modulus of at least 65 kpsi.

33. A golf ball comprising:

-   -   (a) a core having a PGA compression of less than 40;    -   (b) an inner mantle layer;    -   (c) an intermediate mantle layer;    -   (d) an outer mantle layer; and    -   (e) an outer cover layer;    -   wherein the golf ball has sufficient impact durability and a        golf ball frequency of <4000 Hz.

34. The golf ball of paragraph 33, wherein the golf ball frequency isless than 3600 Hz.

35. The golf ball of paragraph 33, wherein the golf ball frequency isless than 3400 Hz.

36. The golf ball of any one of paragraphs 33 to 35, wherein the golfball has a sound pressure level, S, of less than 81 dB.

In view of the many possible embodiments to which the principles of thisdisclosure may be applied, it should be recognized that the illustratedembodiments are only preferred examples and should not be taken aslimiting the scope of the invention. Rather, the scope of the inventionis defined by the following claims. We therefore claim as our inventionall that comes within the scope and spirit of these claims.

What is claimed is:
 1. A golf ball comprising: (a) a core; (b) an innermantle layer, wherein the inner mantle layer comprises a copolymercomprising at least one first co-monomer selected from butadiene,isoprene, ethylene or butylene and at least one second co-monomerselected from a (meth)acrylate or a vinyl arylene; (c) an intermediatemantle layer, wherein the intermediate mantle layer comprises a unimodalionomer; a bimodal ionomer; a modified unimodal ionomer; a modifiedbimodal ionomer; (d) an outer mantle layer, wherein the outer mantlelayer comprises a unimodal ionomer; a bimodal ionomer; a modifiedunimodal ionomer; a modified bimodal ionomer; and (e) at least one coverlayer; wherein the core has a PGA compression of less than 70, and thecore/inner mantle layer/intermediate mantle layer combined construct hasa PGA compression of at least
 40. 2. The golf ball of claim 1, whereinthe inner mantle layer comprises a styrene-butadiene-styrene copolymer,a styrene-isoprene-styrene copolymer, astyrene-ethylene-butylene-styrene copolymer, or astyrene-ethylene-propylene-styrene copolymer.
 3. The golf ball of claim1, wherein the second co-monomer in the inner mantle layer copolymercomprises styrene.
 4. The golf ball of claim 1, wherein the outer mantlelayer has a material flexural modulus of 30-110 kpsi.
 5. The golf ballof claim 1, wherein the core has a PGA compression of less than
 60. 6.The golf ball of claim 1, wherein the core has a PGA compression of lessthan
 50. 7. The golf ball of claim 1, wherein the core has a PGAcompression of 30 to
 40. 8. The golf ball of claim 3, wherein the outermantle layer has a material flexural modulus of 30-110 kpsi and the corehas a PGA compression of 30 to
 40. 9. A golf ball comprising: (a) acore; (b) an inner mantle layer, wherein the inner mantle layercomprises a styrene-ethylene-propylene-styrene copolymer; (c) anintermediate mantle layer, wherein the intermediate mantle layercomprises a unimodal ionomer; a bimodal ionomer; a modified unimodalionomer; a modified bimodal ionomer; (d) an outer mantle layer, whereinthe outer mantle layer comprises a unimodal ionomer; a bimodal ionomer;a modified unimodal ionomer; a modified bimodal ionomer; and (e) atleast one cover layer; wherein the core has a PGA compression of lessthan 70, and the core/inner mantle layer/intermediate mantle layercombined construct has a PGA compression of at least
 40. 10. The golfball of claim 9, wherein the outer mantle layer has a material flexuralmodulus of 30-110 kpsi.
 11. The golf ball of claim 9, wherein the corehas a PGA compression of less than
 60. 12. The golf ball of claim 9,wherein the core has a PGA compression of less than
 50. 13. The golfball of claim 9, wherein the core has a PGA compression of 30 to
 40. 14.The golf ball of claim 9, wherein the outer mantle layer has a materialflexural modulus of 30-110 kpsi and the core has a PGA compression of 30to
 40. 15. The golf ball of claim 9, wherein the outer mantle layer hasa material Shore D hardness of at least 65 and a material flexuralmodulus of at least 65 kpsi.